LANGMUIR-BLODGETT

TROUGHS

OPERATING MANUAL
6th EDITION
Welcome

The information contained within this manual is for guidance only in the use of the product. Since
the product is continually being developed and improved, the information is subject to change
without notice and though given in good faith, may contain errors or omissions.

Nima Technology welcomes any suggestions for further development or improvement of the
product or this manual.

All suggestions and enquiries should be addressed to:

Nima Technology Ltd

The Science Park
Coventry CV4 7EZ
England

Tel: (+44) (247) 641 9457

Fax: (+44) (247) 669 2511
e-mail: info@nima.co.uk
Website: http://www.nima.co.uk

First edition 1989

Second edition 1991 (revised and updated)
Third edition 1992 (revised and updated), 2nd printing 1993
Fourth edition (revised and updated) 1995, 2nd printing 1998
Fifth edition (revised and updated) 1999
Sixth edition (revised and updated) 2001
Software Generation 5.16 for WIN95/98/NT/2000

Authors:

P. Martin and M. Szablewski

Cranfield University
Milton Keynes, England

Editor: Frank Grunfeld, Nima Technology Ltd

Copyright © 1989, 1991, 1992, 1993, 1995, 1998, 1999, 2001 Nima Technology Ltd.

MS-DOS and Windows are a registered trademark of Microsoft Corporation.

IBM is a registered trademark of International Business Machines Corporation.

PageMaker is a registered trademark of Adobe Aldus Corporation.

LabView is a registered trademark of National Instruments Corporation.

ii
 Welcome

WELCOME
Thank you for buying a Langmuir trough from Nima Technology. Our troughs are very versatile,
precision scientific instruments. They can accomplish a wide range of tasks - from the analysis of
lipids and surfactants at the liquid-gas interface to the fabrication of ordered multilayers for
applications in molecular electronics.

With proper care and attention, your trough will be running for many years; and the uses to which
it is put then will be as relevant as they are today.

This manual is divided into several chapters and incorporates everything you need to know on how
to get started in Langmuir-Blodgett (LB) films and using Nima troughs.

There is a 'Langmuir-Blodgettry' chapter which gives a thorough grounding in the principles

involved. Then there is a self-contained 'Tutorial' which takes about a day to work through,
designed to familiarise you with the basic commands of the trough and gain a practical grounding
in LB films. Further understanding of Langmuir films can be gained by working through the series
of experiments contained in the 'Experiments' chapter. A full description of all the trough
commands and functions is given in the 'Software' chapter. Finally a full technical description of
how to set up the motors and sensors is given in the 'Technical Appendix'.

Should any questions arise, please do not hesitate to contact Nima Technology who will be
delighted to help in any way - info@nima.co.uk

Licence Statement

Purchase of a Nima LB trough gives the buyer unlimited licence to copy and disseminate both
information contained in this manual and the software for running the instruments, provided this
is for educational purposes only.

Lifetime Guarantee

Your Nima LB trough is covered by our unconditional lifetime guarantee. This means that if your
trough does not work, we will repair it free of charge, no matter how long after purchase or from
whatever cause, including accidental damage by students. We do however ask that you pay for
the freight charges to and from our workshop in Coventry.

This guarantee does not, however, apply to peripheral equipment, such as PCs, surface potential
sensors & pH meters, made by other manufacturers and consumables such as platinum plates and
rings.

iii
Welcome

CONTENTS
GETTING STARTED .................................................................................... 1

Introduction ............................................................................................................... 2
Unpacking ................................................................................................................. 3
Hardware setup ......................................................................................................... 4
Software installation ................................................................................................ 8
Operation ................................................................................................................... 11
Conclusion ................................................................................................................ 14

LANGMUIR-BLODGETTRY ................................................................... 15

Langmuir films .......................................................................................................... 16

The Langmuir-Blodgett technique .......................................................................... 17
Langmuir films - theory ............................................................................................ 21
Langmuir films - practice ......................................................................................... 26
LB film deposition onto a substrate ......................................................................... 29
Laboratory Requirements ......................................................................................... 33
Bibliography .............................................................................................................. 28

TUTORIAL ................................................................................................... 41

Preparations .............................................................................................................. 42
Producing an isotherm ............................................................................................. 44
Depositing a multilayer LB film .............................................................................. 50
Deposition onto hydrophilic substrates ................................................................... 55
Interpreting transfer ratios ....................................................................................... 57
Operating the trough in 'coupled barrier' mode ..................................................... 59
Operating the trough in alternate layer mode ......................................................... 60
Further Work & Conclusion .................................................................................... 63

EXPERIMENTS .......................................................................................... 65

Preparations .............................................................................................................. 66
A typical pressure-area isotherm .............................................................................. 69
Experiment 1 - Presence of a monolayer ................................................................ 70
Experiment 2 - Molecular flow ................................................................................. 72
Experiment 3 - Area of a molecule ........................................................................... 74
Experiemnt 4 - Collapse of a fatty acid .................................................................... 77
Experiment 5 - Structural changes .......................................................................... 79
Experiment 6 - Acid to salt conversion .................................................................... 81
Experiment 7 - Cholesterol films ............................................................................. 83
Experiment 8 - CMC determination ......................................................................... 85

iv
 Welcome

SOFTWARE ................................................................................................. 87

Introduction .............................................................................................................. 88
Setup Menu ................................................................................................................ 92
Monolayer Menu ....................................................................................................... 94
Dipper Menu .............................................................................................................. 96
Calibrations Menu .................................................................................................... 100

TECHNICAL APPENDIX ........................................................................ 111

Frequently asked questions ...................................................................................... 112

Barrier mechanisms .................................................................................................. 117
Dipper mechanisms ................................................................................................... 122
Pressure sensor .......................................................................................................... 125
Temperature sensor ................................................................................................... 127
Magnetic stirrer ......................................................................................................... 127
Surface potential sensor ........................................................................................... 128
Cable connections ..................................................................................................... 131
Synthesis of ferric stearate ........................................................................................ 132

INDEX ......................................................................................................... 133

v
GETTING STARTED
Getting Started

Introduction
This section describes how to unpack and set up your LB trough. Information is also given about
how to install the software.

Before unpacking your trough, it is a good idea to check that you have everything that you will need
to hand. The following list itemises the minimum laboratory accessories that are required for
efficient operation.

Laboratory Requirements

Bench Space At least 2m in a clean, draught and dust free environment.

Pump Running water and a sink are required for connection of the aspirator
pump provided - alternatively a vacuum pump and Buchner flask can be
used.
Water A supply of pure (deionised and organic free) water is required for
troughs. Recommended manufacturers include Elga, Millipore and
Barnstead.
Balance To be capable of measuring accuracies of at least 0.1mg.
Sundries Polythene powder-free gloves, surfactant-free, lint-free tissues (supplied),
cleaning solvents (e.g. chloroform), small volumetric flasks (10ml).
PC A Pentium PC running WIN95 or higher. The Nima software occupies
less than 10MB of disc space. A free serial port is essential to communicate
with the serial interface.

2
 Getting Started

Unpacking
Before unpacking, make a visual check of the packaging. Make a note of any obvious damage.
During unpacking, look at each item carefully, identify it (most items are labelled) and check
that it looks undamaged.

In the event of damage, notify Nima Technology and the freight agent immediately. It is a
good idea to take pictures of the damaged packaging and goods at this stage - this will help
any insurance claims and speed replacement of damaged items.

You should find some or all (depending on what type of trough you have) of the items below in
the crate your instrument was shipped in:

* Langmuir trough

* Dipper mechanism (optional - conventional and/or alternate layer) for dipping troughs

* Pressure sensor(s) (2 for alternate layer troughs, Models 622D2)

* Interface unit, serial cable and mains lead

* 2 discs with the operating software

* Monolayer kit
- plastic box with small compartments containing the following:
tweezers, pointed
tweezers, flat (for dipper trough only)
10, 50 or 100µl syringe (depending on size of trough)
spatula
balance pan, pan carrier & 100mg calibration weight
bag of hooks
bag of paper Wilhelmy plates
miniature tools
chromed aspirator pump
PTFE nozzle for aspirator pump

* Box of 'Kimwipe' tissues - type 7105

* Packet of polythene, powder-free gloves,

* Rubber tubing for aspirator pump.

* This manual!

Take care when unpacking your Nima LB trough - it is a precision piece of machinery
made by craftsmen. Take exceptional care when unpacking the pressure sensor, as this
is the most delicate part of the system.

3
Getting Started

Hardware setup

Locate a quiet, clean corner of your lab, free from air currents. You will need about 2m of bench
space and a comfortable chair to sit on. These measurements need plenty of patience and an
uncomfortable student is a sloppy researcher.

Access to running water (to connect the aspirator) is recommended. Alternatively, using a vacuum
source and Buchner funnel is also recommended.

Please identify your trough from the diagrams below and set it up as shown:

Figure 1.1: 601M

Pressure sensor mounted on edge of trough (A) or on separate stand (B)

2 mechanically coupled barriers
Sapphire window (removable with locking key)
Tubing connectors for temperature control

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 Getting Started

Figure 1.2: Models 601S & 601A

Pressure sensor at one end of the trough

1 or 2 barrier(s)
Acrylic, hinged cover
Tubing connectors for temperature control

Figure 1.3: Changing or replacing removable top on base

Most troughs have removable tops for easy cleaning.

These just lift off.

5
Getting Started

Figure 1.4: Models 611M & 611D

Dipper
1 or 2 barriers
Pressure sensor
Well all at one end or in centre
Hinged cover
Tubing connectors for temperature control

Figure 1.5: Model 622D2/D1

2 compartment trough with 2 pressure sensors

Alternate layer dipper mechanism (A)
or conventional dipper (B) B
2 hinged covers
2 temperature control circuits.

6
 Getting Started

Levelling & temperature contol

Nima troughs are levelled by means of the four adjustable legs which support the trough.

For temperature control, you can connect suitable tubing to the troughs now or later. The troughs
come with standard fittings which can be unscrewed if you prefer your own.

Pressure sensors

The pressure sensors on troughs use a Wilhelmy plate (in this case, a small length of chromatog-
raphy paper - Whatmans Chr1) to measure the surface pressure (reduction in surface tension).

For each pressure sensor, take 2 or 3 'S' shaped hooks from the monolayer kit and attach them
in 'daisy chain' fashion to the small wire protruding from the pressure sensor. Take one of the pre-
cut Wilhelmy plates provided, thread one of the hooks through the hole punched in it, and attach
it to the lowest hook already suspended from the pressure sensor.

Interface Unit

The unit is supplied with a universal mains adaptor for 100 - 240V, 50/60Hz. Connect the three
pin mains lead into the mains adaptor and the 6mm jack into the 'DC in' socket of the interface.
Do not switch on yet.

Connect the round 5 pin DIN plugs to the back of the interface unit. These are marked 'BAR-
A' for barrier A, 'BAR-B' for barrier B (if you have one), 'PA' for pressure sensor A, 'PB' for
pressure sensor B (or tensiometer), 'LIN-DIP' for a conventional linear dipper and 'ALT-DIP'
for an alternate dipper.

Attach the serial cable to the interface unit (IU4) and to the serial port of the PC - the interface
end is a 9 pin 'D'. The PC end is also 9 pin D and a 25-9 way converter is also supplied.

If you are using a mouse on a serial port, you must use a different port for the interface. However,
beware(!) because some mouse software drivers clash with the trough serial port driver. Check
in your WIN Control Panel under:

System / Device Manager / Ports / Resources / Interrupts

7
Getting Started

Software Installation
Notation and computer literacy

A certain familiarity with computers and WIN95 is assumed. You must know the correct way to
insert a floppy disc into your personal computer (PC) and you must understand what a file is and
what a directory is. You must also be able to 'Run' programs in WIN95. It is also helpful if you
know how to change icons.

If you are not happy with these ideas, we suggest that you consult the manuals of your
computer and software vendor. There are probably also a wide range of help manuals
available at your university bookshop.

PC requirements

You need to have a Pentium PC running WIN95 or higher.

Your PC has to have a free serial port to communicate with the Nima interface.

Please set the Display to a minimum of 800 x 600 pixels. This can be changed under:

Start / Settings / Control Panel / Display / Display Modes.

Software organisation

There is one main program which controls all the functions of the instrument:

- Nima516.exe where '5' is for the 5th generation and the 16 is the version number.
This is the standard software for Langmuir troughs.

There are also files containing data which the main program needs before it will run. These initially
hold 'standard' data which you can alter as you go. These are:

install.dat This contains all the installation data for your trough.

sensors.cal This contains all the calibration data for your sensors.

standard.con This contains a standard set of operating conditions.

And finally there is:

serpdrv This is the serial port driver which allows communication between
your PC and the interface unit (IU).

All these files must be located in the same directory. The default directory is C:\nima, but any other
directory can be used.

8
 Getting Started

Installation from disk

Insert disk 1 into drive a and select Run from Windows Start Panel. Enter a:\setup.exe in the
Open box and the software will prompt you to load into c:\nima .You can choose a different
directory at this stage. Then the Install Wizard will take over - just click on the 'finish' button
to start (Microsoft Logic!).

If you have problems, such as 'unable to find disk 2', please copy the 3 files: 'setup.exe', 'data.001'
and 'data.002' into the 'c:\windows\temp' directory and run 'setup.exe' from this directory, using
the 'Run' command.

A shortcut to the Nima516.exe will be displayed in a Nima group file window. If you want to use
the 'Nima' icon, use the right hand mouse button to click on the shortcut file to change its properties
and select the 'trough.ico' icon.

Installation from the website

Click on the 'Software' button in the margin on the left side of our home page. The instructions for
downloading are given on the screen. Very briefly, these consist of:

1. Download - just click on 'download' and the 'zipped' file (2MB) is loaded onto your PC.
2. Unzip - using WinZip, unzip the file into its 3 constituents.
A link to www.winzip.com is given, if you don't have this program.
3. Setup - as above - 'Installing from disk'.

Running

Double click on Nima516.exe to run it (or on its shortcut if you have placed it on your desktop).
'OK' the introduction window and a set of pressure-area axes will be displayed with a menu bar
along the top, as in the figure below. Note that an isotherm is displayed only if the interface is
disabled.

Figure 1.6: Main screen of Nima software

9
Getting Started

Setting up the Interface

Before anything else, please click on 'File' in the menu bar and 'Setup' to enter the 'Setup Menu'.

Select the port you think you are using (if in doubt, start with port 1) and enable the interface. If
the V2 light on the interface illuminates, then communications have been established successfully.
If nothing happens, change the port number to '2'. Usually, PCs use port 1 or 2 for the external
serial port connections. If you still have trouble you can try port 3 or 4, but it is unlikely they are
being used. Take care, if your PC is not configured for port 3 or 4, the program may hang up and
you will have to press CTRL-ALT and DELETE to start again!

If you continue to have problems, please check that there is not a clash with other serial devices,
such as mouse drivers and networks. You can look at your port settings in the WIN Control Panel
under:
System/Device Manager/ Ports

Once communications have been established, click on the 'ACCEPT' button and the calibration
file is updated automatically, so that the next time you launch the program, the correct serial port
will be addressed immediately.

Setting up for 2 operating modes or multiple users

If you have a trough like the 632D1D2, then it is possible to run this in 2 modes - either with the
conventional dipper D1L or with the alternate layer dipper D2.

The simplest way to switch between operating modes in the software is to install both versions of
the software (which are supplied) into different directories. For example, you can make a directory
called 'ConLB' for the conventional dipper and a directory called 'AltLB' for the alternate layer
software.

If you then make shortcuts for the two different Nima516.exe files, you can run one or the other
at the click of your mouse. Do not run both simultaneously, as the serial port drivers will clash -
unless, of course, you have 2 serial interfaces running 2 troughs.

10
 Getting Started

Operation
There are 'one click' buttons for basic functions like 'opening' and 'closing' the barrier. These are:

O Open barrier
C Close barrier
D Dipper down
U Dipper up
STOP Stop all motors
CLEAR Clear data from memory

F Dipper forwards (alternate layer troughs only)

B Dipper backwards (alternate layer troughs only)

Other commands are embedded in the menus along the top of the screen:

File (f1) - this gives access to the Save, Load and Setup Menu. Also to Exit the program.

Graph (f2) - the data can be displayed as a pressure-area isotherm, pressure & area v time,
immersion depth-area or transfer ratios.. Select the appropriate display from the Graph
Menu. Axes are auto-scaled but may be manually re-scaled by right clicking anywhere on the
graph and then typing over axes labels.

Barrier Menu (f3) Selects the barrier mode you require: Choose between Monolayer Menu,
Open, Close, Isotherm or Pressure (Pi) Control, Isotherm cycle, Coupled Mode and Area
Control.

Dipper Menu (f4) - Selects the dipper mode you require - Choose between Dipper Menu, Up,
Down (Forwards or Backwards for alternate layer dipper), Programmed Dip and Creep Up
or Down

Run time variables (f7 - separate box at top left of screen) - allows important values to be
changed before or during a run. Choose between Target Pressure, Feedback Gain, Immerse
To, Raise To, Cycle Max Area and Cycle Min Area.

The STOP button can also be accessed from the 'ESC' key.

Typical operating sequences for taking a pressure-area isotherm and depositing an LB multi-layer
are given overleaf.

11
Getting Started

A typical pressure-area isotherm

The following steps are recommended to take an isotherm:

1. Clean the trough thoroughly with a Kimwipe (soaked in chloroform). Ensure you are
wearing the polythene gloves provided and working in a well ventilated area.

2. Make up a solution of 1mg/ml arachidic acid in chloroform.

3. Fill the trough with clean water.

4. Close the barrier(s) by clicking on 'C' - or the 'home' button of your keyboard.
- the barrier(s) will move to their 'close-to' position.

5. Aspirate the surface of the water enclosed by the barrier(s).

- keep your eye on the pressure reading - this will drop as the water level reduces and
is cleared of surfactants.

6. Open the barrier(s) by clicking on 'O' - or the 'end' button of your keyboard.
-the barriers will move to their 'open-to' position.

7. Zero the pressure sensor by clicking on 'Z'

- the current surface tension (~72.8 mN/m) will be defined as zero surface pressure
i.e. 0 mN/m.

8. Take an isotherm without molecules by clicking on 'Barrier' and 'Isotherm'

- the barriers will close and the isotherm will be displayed on the screen.
If it the trough is clean, the curve will be horizontal along the X-axis. If there are
surfactants on the surface, a small rise in pressure will be observed at smaller
areas.
Please note that the axes are set to 'auto-scaling' and adapt themselves to the data
recorded, so at first the data will appear greatly magnified.

9. Clean the surface again with the aspirator.

10. Zero the pressure sensor.

Whenever some water has been sucked out of the trough, it will have to be re-zeroed.

11. Open the barriers and spread the solution from the micro-litre syringe.
Wait for the pressure to return to 0mN/m - this indicates that the solvent has
evaporated. If the pressure does not return to zero, you have spread too much and
will have to remove some monolayer with the pump.

12. Take the pressure-area isotherm

- you should now see a good pressure area isotherm of arachidic acid on water.
For an example of such an isotherm, please see the graph in Figure 1.6.

13 Stop the barrier by clicking on 'STOP' - or the 'Esc' key on your keyboard.
If you do not, the barrier will continue until it passes its 'close to' area and then
a message saying 'barrier too closed' will appear. The barrier will then be stopped
automatically.
12
 Getting Started

A typical multi-layer deposition (conventional dipper)

1. Follow the instructions for the pressure-area isotherm first (previous page).
This will ensure that the trough is clean and ready to go.

2. Make up a solution of 10-4M ZnSO4 from the chemicals supplied with the trough.
Make enough to fill your trough about twice.

3. Prepare a glass slide by rubbing it with the ferric stearate supplied.

This will make it hydrophobic.

4. Move the dipper up by clicking on 'U' - or the 'PgUp' button of your keyboard.
The dipper will come to rest at its top position.

5. Insert the slide between the jaws of the dipper clamp.

6. Go the Dipper Menu ('Dipper' on menu bar).

7. Select the appropriate values for your deposition.

Typical values are: Dipper Speed: 20 mm/min

Target pressure: 25 mN/m
Top End: 5 mm
Bottom End: 20 mm
Number of Layers: 10

8. Spread the monolayer and select 'Pressure Control' from the Barrier menu.
The film will be compressed to its target pressure. If pressure control is unstable,
reduce the 'Feedback Gain' value (Variables menu - top left of screen). A value of
1.0 is good for almost all conditions.

9. Select 'Program Dip' from the Dipper menu

The dipper will be run down and up under the selected conditions.

10. When the required number of layers have been deposited, the dipper will stop.

11. Data can be viewed also in the (pressure & area) -time and dipper - area axes, selected
from the Graph Menu.

Saving / Loading (File Menu - f1)

Saves and loads data as ASCII files with *.txt extension. These can be imported into most
spreadsheets.

Copying, pasting & printing

Copy to pasteboard by hitting the 'ALT-Print Screen' keys on your PC. Paste into other
applications (e.g. Word, PageMaker) - the graph will be pasted as it appears on the screen. Print
out in the usual way.

13
Getting Started

Conclusion
By now you should have assembled your Nima LB trough, and carried out some simple checks
to establish that it is operational.

The following chapters of this manual will give a thorough introduction to the theory and
practice of Langmuir-Blodgett films.

14
 LANGMUIR
BLODGETTRY
Langmuir Blodgettry

Introduction
This section deals with the theory and practice of Langmuir Blodgettry. It covers the materials used
- solvents, water, chemicals and substrate - and their preparation as well as cleanliness and safety.
It also provides a comprehensive account of the practice of Langmuir Blodgettry - its history, the
subphase, spreading, isotherms and dipping.

Langmuir films
Langmuir films consist of surface active materialsor 'surfactants' trapped at the interface between
two dissimilar phases, either liquid-liquid or liquid-gas.

Surfactants are molecules which are amphiphilic, that is molecules which are composed of a
hydrophilic part and a hydrophobic part. Hydrophilic groups consist of groups such as carboxylic
acid, sulphates, amines and alcohols. These are all attracted to polar media such as water and the
forces acting upon them are predominantly coulomb type (1/r²). Hydrophobic (or oleophilic)
groups such as a hydrocarbon chain, fats and lipids are much less (if at all) water soluble and the
forces acting upon them are predominantly van der Waal's type (1/r12 and 1/r6). Amphiphilic
molecules are trapped at the interface because they posses these two very different types of
bonding within the one molecular structure.

When surfactants, dissolved in a non-aqueous volatile solvent, are introduced onto a polar liquid
surface, the solvent will evaporate leaving the surfactants oriented at the liquid-gas interface. The
hydrophilic 'head' groups pull the molecule into the bulk of the water and the hydrophobic 'tail'
groups point into the air. A surface monolayer will only be achieved if the amphiphatic balance of
the molecule is correct; that is the balance between hydrophobic and hydrophilic parts. If the
hydrophobic 'tail' group is too short (not hydrophobic enough) the molecule will be dragged into
the water and will dissolve while if there is no hydrophilic part, the molecules may form thicker
multilayer films on the surface or even evaporate.

Sweeping a barrier over the water surface causes the molecules to come closer together and
eventually to form a compressed, ordered monolayer - much like forcing together balls on a billiard
or pool table. The film produced by such a method is known as a Langmuir film.

Figure 3.1: Expanded and compressed monolayers on a water surface

16
 Langmuir Blodgettry

The Langmuir-Blodgett technique

Langmuir-Blodgett films consist of mono-molecular layers stacked sequentially onto a solid

substrate. A solid substrate is lowered into the water, breaking through the Langmuir film and,
provided that certain criteria have been met, the Langmuir film attaches itself to the substrate,
coating it in a mono-molecular layer.

Once the first layer has been deposited, further layers will be deposited on each subsequent pass
of the substrate through the air-water interface. Multilayers can therefore be deposited to produce
a film, the thickness of which is the product of the individual molecular chain length and the number
of times that the substrate has crossed the air-water interface.

Figure 3.2: Deposition of the first monolayer onto a hydrophobic substrate.

Figure 3.3: The substrate reverses (a) and the second layer is deposited (b).

17
Langmuir Blodgettry

History and development

The effects of oils on water surfaces have been known for many centuries. Babylonians in the
eighteenth century BC have been recorded as practising divinity by observing the effects of oils
spread on water. The Japanese printing art of sumi-nagashi (black-ink-let-flow) is one of the first
technical applications of floating monolayers. A suspension of sub-micron carbon particles and
proteins are spread on a water surface and subsequently covered with gelatin to create patterns
which can then be transferred onto a sheet of paper lowered onto the surface. The traditional craft
of 'marbling' also works on a similar principle - paint is dispersed on an aqueous surface and a piece
of paper is drawn up out of the water to be covered by the pretty patterns created.

Scientific interest
The first scientific interest in mono-molecular layers was shown by Benjamin Franklin (during a
visit to London to discuss certain colonial matters) when he spread oils onto the pond at Clapham
Common and observed that the one teaspoon full of oil which he used had a calming influence over
half an acre of water. Taking '1 teaspoonful' to be 5ml, this would mean that a film of thickness
2.5 x 10-7m (about 100 layers) was covering the 'half an acre' (2,000m²). Franklin reported his
findings to the Royal Society of London in 1774:

Figure 3.4: Part of Benjamin Franklin’s original paper

18
 Langmuir Blodgettry

Modern investigations of molecular films began with Agnes Pockels experimenting with a very
simple trough in her kitchen. Her ideas, expressed as letters to Lord Rayleigh, were published in
'Nature' in 1891. She realised the importance of cleanliness and developed many of the techniques
which are regarded as standard today. Her experiments included the first containment of a
monolayer by means of a barrier.

Further investigations carried out by Rayleigh, Devaux and Hardy confirmed the mono-molecular
nature of such films. However it was Irving Langmuir who contributed the greatest advances,
building on many of the ideas of Pockels and others to publish 'The Constitution and Fundamental
Properties of Solids and Liquids' in 1917 which described the 'new' surface effects. Langmuir
studied the pressure-area relationship of molecules on an aqueous surface. The areas occupied
by molecules such as acids, alcohols and esters were found to be independent of the hydrocarbon
chain length, thus showing that only the hydrophilic head groups were immersed in the subphase.

Katherine Blodgett, who worked with Langmuir on the properties of floating monolayers,
developed the technique of transferring the films onto solid substrates and hence building
up multilayer films. Her results were published in 1934 and 1935, culminating in a paper with
Langmuir in 1937 and a paper on anti-reflection coatings in 1939 (see the 'Tutorial' chapter).

Langmuir-Blodgett films have been used in some practical devices. The first, developed by
Blodgett, were the above mentioned anti-reflection coatings, and step thickness gauges.

The recent past and the future

Interest in Langmuir-Blodgett films subsided with the outbreak of the Second World War,
and remained low until the 1960’s when Kuhn and Möbius showed how monolayers could
be used to construct precise supermolecular structures. They used the Langmuir-Blodgett
technique to demonstrate the fluorescence and quenching of dye molecules attached to fully
saturated fatty acids under ultraviolet light. This work and the publication of Gaines' 'Insoluble
Monolayers at Liquid Gas Interfaces' in 1966 initiated a revival of interest in the field.

Many possible applications of Langmuir-Blodgett films in the fields of electronics, optics,

molecular electronics and biotechnology are currently being investigated by research groups
throughout world. Some examples are:

Biology: Cure for 'blue baby' syndrome. Some babies are born without the ability to breathe.
This is because their lungs cannot absorb oxygen just after birth. Surfactants are being developed
to be sprayed into the lungs to absorb oxygen. Once this process is stimulated, it is self
regenerating. Surfactants are being designed by testing Langmuir monolayers for this oxygen
absorbing ability.

Chemistry: Sensors - to have chemical sensors (such as gas detectors) it is best to have a large
surface to bulk ratio. This gives higher signals for lower concentrations of gas and can improve
reversibility of the detection process. LB layers are ideal candidates.

Physics: Optical waveguides and devices are being developed for computing and communications
applications. The capability of fabricating dimensions to mono-molecular tolerances and their
ability to incorporate different molecular architecture give LB films some unique advantages in this
field.

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Langmuir Blodgettry

The original troughs

Trough design has changed markedly since the early waxed troughs used by Langmuir, Schaefer
and Blodgett. These were ordinary baking trays (purchased at the local hardware shop) that were
waxed to make them hydrophobic. They were filled to the brim with water - this allowed for easy
cleaning of the surface by simply sweeping a bar along the ridges formed by the trough walls. Films
were confined by floating a length of waxed silk on the water surface thus dividing the surface into
two compartments. One of the compartments was filled with piston oil of known surface pressure
which compressed the monolayer, spread in the other compartment, to a pressure which would
remain constant throughout the experiment. Contamination of the monolayer under study and the
preparation of the waxed silk were the major problems. This prompted the development of new
barrier systems which would eliminate such problems.

Gaines gives an example of a rectangular trough with a boom which moves along the top of the
trough walls (the trough being filled to the very brim) by means of suspended weights attached to
the barrier through a pulley system. There was no cross-contamination problem as no piston oil
was involved but the gravity driven barrier did not allow easy measurement of the surface
pressure-area characteristics. Although all these troughs required considerable experimental skills
to operate successfully, Blodgett was able to build up thousands of layers at speeds of up to twenty
layers per minute using such apparatus.

Figure 3.5: Langmuir’s film balance

Reprinted with kind permission from the Journal of the American Chemical Society,
1917, Vol 39, pg 1869, Copyright 1917, The American Chemical Society.

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 Langmuir Blodgettry

Langmuir films - theory

Spreading
The monolayer is formed on the surface of the subphase by dissolving the amphiphilic substance
in a suitable solvent - see also the section on 'Solvents' later in this chapter - and spreading the
resulting solution dropwise on to the water surface.

The spreading solution is best applied to one point of the surface by allowing small drops to fall
from the syringe while it is held a few millimetres above the sub-phase. Each drop should be
allowed to evaporate before the next is applied. An alternative procedure that is used for
molecules known to form more rigid films, involves distributing the drops equally over the entire
surface of the sub-phase.

The process of spreading can occur in a number of ways. Usually a thin film is formed by the
spreading solution while the Langmuir film forming material attains its favoured configuration at the
air-water interface and the solvent evaporates, leaving behind only the monolayer. In some cases
the deposited droplet does not spread over the subphase but instead a thin film of dilute solution
of monolayer-forming material spreads from its edges; as solvent evaporates, more film spreads
from the droplet. As most solvents used are slightly soluble in water, depletion of the spreading
solvent will not be due exclusively to evaporation but also to some dissolution of it into the
subphase.

Spontaneous spreading will continue until the surface pressure of the monolayer is equal to the
'equilibrium spreading pressure'. At this point, all the available surface is covered in monolayer and
any further droplets of solution remain embedded in the monolayer as floating lenses, as no more
spreading out can take place. Any undispersed material must be removed otherwise it may be
deposited as bulk aggregates on substrates dipped into the monolayer.

Isotherms
Molecules in a solution are subject to attractive forces; in the bulk of the solution these forces are
equal. However, at a surface or interface the forces are unequal and the net effect is to pull the
peripheral molecules into the bulk of the solution. This effect gives rise to surface tension.

The surface tension can be defined as 'the work required to expand the surface isothermally by
unit area' . The tendency of surface-active molecules to accumulate at interfaces favours expansion
of the interface and hence lowers the surface tension. Such behaviour makes it possible to monitor
the surface pressure as a function of the area occupied per molecule provided that the number of
molecules deposited on the surface is known.

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Langmuir Blodgettry

The characteristics of a monolayer on the water surface are studied by measuring the changes in
surface tension upon compressing the monolayer. The reduction of surface tension is known as
the surface pressure. Pressure readings are made by means of 'Wilhelmy' plates attached to a
microbalance (see 'surface pressure measurement', later in this chapter). The plot of surface
pressure versus area occupied per molecule is known as a 'pressure-area isotherm' - isotherm
because compression takes place at constant temperature. The shape of the isotherm is
characteristic of the molecules making up the film and hence provides a two-dimensional
'fingerprint'.

Forces at the subphase surface

The forces affecting the polar head groups submerged in the aqueous subphase are ionic and
proportional to 1/r2 ('r' being the intermolecular separation) whilst the forces between the
hydrocarbon chains are due to van der Waal’s interactions and proportional to 1/r6 and 1/r12.
Hence the interactions in the subphase are of longer range than those in the superphase. The
isotherm can usually be seen to consist of three distinct regions:

Figure 3.6: A stearic acid isotherm on pure water

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 Langmuir Blodgettry

After initial spreading onto the subphase, no external pressure is applied to the monolayer and the
molecules behave as a two-dimensional gas, which can be described by:

πA = KT

where π is the surface pressure, A the molecular area, K the Boltzmann constant and T is the
thermodynamic temperature. On compression of the monolayer, some ordering of the film takes
place and it behaves as would be expected of a two-dimensional liquid.

With continued closing of the barrier, the increase in pressure causes additional ordering, the
monolayer behaving as a quasi-solid. This solid state is characterized by a steep and usually linear
relationship between surface pressure and molecular area.

Eventually the collapse pressure, πc, is reached at which the film irretrievably loses its mono-
molecular form. The forces exerted upon it become too strong for confinement in two dimensions
and molecules are ejected out of the monolayer plane into either the subphase (more hydrophilic
molecules) or the superphase (more hydrophobic molecules). However, collapse is not uniform
across the monolayer but is usually initiated near the leading edge of the barrier or at discontinuities
in the trough - such as corners or the Wilhelmy plate. Usually a 'collapsed' film will consist of large
areas of uncollapsed monolayer interspersed with 'mountain ridges' where monolayers have been
crushed together to form bulky aggregates. This is rather like mountain formation at the collision
of the earth's tectonic plates, but on a vastly different scale.

The collapse pressure can be defined as the maximum to which a monolayer can be compressed
without the detectable expulsion of molecules from the Langmuir film. It depends upon the details
of the experimental procedure used, i.e. the chemical substances used, the temperature, the rate
at which the film is compressed and procedures to which the film has been subjected. The value
of the collapse pressure for a simple saturated fatty acid can be in excess of 50mN/m which is
equivalent to about 200 atmospheres if extrapolated to three dimensions.

Quantitative information can be obtained on the molecular dimensions and shape of the molecule
under study. When the monolayer is in the two-dimensional 'solid' or 'liquid condensed' phase the
molecules are relatively well oriented and closely packed and the zero-pressure molecular
area(A0) can be obtained by extrapolating the slope of the 'solid' phase to zero pressure - the point
at which this line crosses the x-axis is the hypothetical area occupied by one molecule in the
condensed phase at zero pressure (see Figure 3.5). For a fully saturated alkanoic acid such as
stearic acid the molecular area determined in such a manner is 22-25 A2. Such an area
corresponds to the cross-sectional area of a hydrocarbon chain, suggesting that the compressed
monolayer consists of close packed vertically orientated chains. The Nima software calculates this
zero-pressure molecular area(A0) for you - as described in the 'Tutorial', later in this manual.

It is important to study the isotherm of the monolayer of the film forming material as a pre-requisite
to the determination of dipping characteristics. Information can be obtained as to the way in which
the molecules pack at the interface and the stability of the compressed layer at high pressures.
Improved quality can be obtained by 'annealing' the film, that is by compressing (never going above
πc) then expanding a number of times. Such a procedure encourages more efficient packing and
usually a shift to lower molecular areas is observed. Recent work suggests that the Langmuir film
exists in a number of different liquid crystal phases on the water surface, depending on the film
temperature and pressure.

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Langmuir Blodgettry

Surface pressure measurement

Any liquid will always try to reduce its surface area - this is known as surface tension. The higher
the surface tension of a liquid the less it will spread out - just think of a droplet of mercury on a
clean surface and compare it to water or oil.

Surface pressure is the inverse of surface tension. Imagine a clean water surface - under ideal
conditions this has a surface tension of 72.8mN/m. Its surface pressure will be 0 mN/m. If we now
spread a contaminant on the water surface (either some dust or some surfactants), the surface
tension may drop to 52.8mN/m. The surface pressure will have risen to 20mN/m.

Surface pressure on Nima trough is measured by the Wilhelmy plate. The Wilhelmy plate is a strip
of chromatography paper (Whatman's Chr 1) which, when suspended at an air-water interface,
is pulled down into the bulk of the subphase by the surface tension of the water.

The forces upon the plate are gravity and surface tension acting downwards into the subphase,
and buoyancy due to displaced water acting upwards.

Figure 3.7: The Wilhelmy Plate

If the plate has dimensions l x w x t (length, width, thickness) and a density, ρ, and is immersed
in water to a depth, h, then the net force downwards, F, is described by the equation:

ρPlwt).g - (ρ
Force = (ρ ρLhwt).g + 2.(w+t).(ST).cosØ Eq.1

(Force = weight - upthrust + surface tension )

where ρP is the density of the plate, ρL the density of the liquid, ST the surface tension of the
liquid, Ø the contact angle of liquid to plate and g the acceleration due to gravity.

Before making any measurements, the pressure reading is zeroed, thereby eliminating the weight
term from Eq.1:

ρLhwt).g + 2.(w+t).(ST).cosØ
Force = - (ρ Eq.2
(Force = - upthrust + surface tension)

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 Langmuir Blodgettry

The upthrust term is eliminated from Equation 2 as the plate is always kept at a constant level by
the balance, no matter what the surface tension:

Force = 2.(w+t).(ST).cosØ Eq.3

Finally, use of paper plates ensures a contact angle of liquid to plate of 0° and the expression
reduces to:

Force = 2.(w+t).(ST) Eq.4

Hence for a plate, the surface tension is:

STplate = Force / 2.(width + thickness) Eq.5

where surface tension is in mN/m, force in mN and perimeter in metres.

Generally therefore, the surface tension is given by:

ST = Force / perimeter Eq.6

Thus for a ring, the surface tension is given by:

πd + π(d-2t) )
STring = Force / (π Eq.7

where 'd' is the outer diameter of the ring and 't' is the thickness of the wire in metres. Surface
tension is in mN/m and force is in mN.

Hence for a 10.25mm wide, 0.25mm thick paper plate, a 100mg weight will give a reading of
46.7mN/m. This is useful figure when you are checking your pressure sensor.

Note that: 1 dyne/cm = 1 mN/m.

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Langmuir Blodgettry

Langmuir films - practice

Materials suited to the LB technique

The LB technique, by definition, requires amphiphilic molecules to be trapped at the interface of
two phases (either liquid-liquid or liquid-gas). For the molecules to be trapped at the interface,
the 'amphiphatic balance' i.e. the balance between the hydrophilic and hydrophobic constituents
within the same molecule must be correct for the two phases concerned. For instance, the
amphiphatic balance of a molecule may be correct for an air-water interface but not for an water-
hexane interface. Hence, when choosing materials, this factor has to be taken into account.

In practice, monolayer and deposition criteria are not so exacting, as many researchers have
produced excellent multilayer films using the LB technique with molecules that have only a very
small hydrophilic component and that literally float on the water surface. Strictly speaking though,
these are not LB films.

In general, materials such as long chain fatty acids and alcohols are used as film forming materials.
The hydrocarbon part -CH2- of the molecule is responsible for the material's repulsion of water
while the polar -COOH or -OH group has sufficient affinity for water to anchor the molecule in
the aqueous subphase.

At an air water interface such amphiphilic molecules orient themselves with their hydrocarbon
chains upwards in the air and their hydrophilic head groups downwards into the aqueous phase:

Figure 3.8: Fully saturated fatty acid (stearic acid). 'Fully saturated' signifies that all
the available carbon bonds have been taken up by hydrogens

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 Langmuir Blodgettry

The materials which have been studied extensively as floating monolayers are the alkanoic acids
and their salts and long chain alcohols. The length of the hydrocarbon chain is critical and its effect
on the surface tension of the subphase is given by Traube’s rule, an approximation which states
that for a given homologous series of amphiphiles the concentration required for an equal lowering
of surface tension in dilute solution decreases by a factor of about three for each additional CH2
group.

The effectiveness of functional groups attached to the hydrocarbon chains in providing attraction
to an aqueous subphase is summarised in the table below:

No film Unstable films Stable film with C16 chain com-

C16 chain pounds dissolve
Hydrocarbon -C6H4OCH3 -CH2OH -SO3-
-CH2I -COOCH3 -COOH -OSO3-
-CH2Br -CN -C6H4SO4-
-CH2Cl -CONH2 -NR3+
-NO 3 -CH=NOH
-C6H4OH
-NHCONH2
-NHCOCH3

Table 3.1: Commonly used film forming materials

The types of materials listed above are those which have been extensively studied over the years
and are regarded as the classic Langmuir-Blodgett film forming materials. However, current
interest is primarily due to the introduction of 'active' molecules such as chromophores or
biologically functional molecules into monolayer films. Although traditionally long hydrocarbon
chains have been considered necessary, the incorporation of aromatic moieties and unsaturated
chains into the amphiphile tends to decrease the hydrocarbon chain length necessary for
deposition. For example, a substituted anthracene derivative has been successfully deposited with
only a butyl chain attached to the polyaromatic system. In fact, with appropriate synthetic
chemistry almost any active species can be tailored into a form which will float as a monolayer.

The subphase
The subphase most used for the study of mono-molecular films is ultra pure water. Other high
surface-tension liquids which have been used as subphases include ethylene glycol, glycerol and
mercury.

Usually measures are taken to exclude any contaminants from the subphase as the introduction
of ions into pure water can dramatically affect the monolayer properties. For example, the
repulsion between adjacent ionised acid groups can be reduced by the addition of divalent
metal ions into the water. Introducing Zinc (Zn2+) into the water results in following reaction
taking place:

27
Langmuir Blodgettry

R R R R

C C + Zn2+(aq) C C

O O- O O- O O O O
Zn

Table 3.2: Reaction of Zn2+ with an alkanoic acid group

Care must be taken in making up the solutions - high quality reagents and ultra-pure water must
be used. Moreover, it should be remembered that the aqueous subphase consists of a number of
variables, not necessarily independent of one another. A change in one ionic equilibrium will often
affect several of the other equilibria within the subphase.

Changing the acidity and adding divalent ions to the subphase allows a considerable degree of
control over monolayer behaviour and the successful deposition of multilayers.

5H2O ⇔ 5[H+ + OH-] ⇔ [H9O4]+ + OH-

CdCl2 ⇔ Cd2+ + 2Cl-
ZnSO4 ⇔ Zn2+ + SO4-
NaOH ⇔ Na+ + OH-
HCl ⇔ H+ + Cl-

Table 3.3(a) Typical ionic equilibria in the aqueous subphase:

Primary dissociations i.e. equilibria of ionic species introduced into the subphase.

Zn2+ + 2OH- ⇔ Zn(OH)2

Cd2+ + 2OH- ⇔ Cd(OH)2
Na+ + Cl- ⇔ NaCl

Table 3.3(b) Typical ionic equilibria in the aqueous subphase:

Secondary dissociations i.e. equilibria set up between ions introduced from differing
sources. The addition of chloride ions to the subphase can reduce the pH as this results
in hydroxide ions being taken out of the subphase.

Buffers should only be used in biological applications and not for making LB films, as they
introduce new unknowns into the subphase.

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 Langmuir Blodgettry

LB film deposition onto a substrate

Two types of surfaces can be coated by the LB technique - hydrophobic (water repelling) and
hydrophilic (water attracting). Deposition onto a hydrophobic surface always takes place on the
down path while for a hydrophilic surface, deposition always takes place on the up path.

The surface of a substrate being coated with a LB film changes from hydrophobic to hydrophilic
with every layer. Thus when a hydrophobic surface is immersed and coated with a monolayer, it
will be completely hydrophilic while it is immersed. Then, when it is withdrawn from the
subphase and a second layer is deposited, the surface will be hydrophobic again.

Figure 3.9: Deposition of the first 2 layers. The immersed surface of the substrate becomes
hydrophilic after deposition of the first layer and becomes hydrophobic again after
deposition of the 2nd layer. Note that the second layer does not start deposition until the
meniscus is 'flipped' over.

Hence, for deposition to occur, the prime criterion is that the curvature of the meniscus at the liquid/
substrate boundary and the direction of motion coincide.

It is easy to determine what type of surface you have - just immerse the substrate in the subphase.
If the meniscus curves down, the surface is hydrophobic - if it curves up then the surface is
hydrophilic.

A hydrophobic substrate will result in deposition on the first down pass, the hydrophobic
hydrocarbon tails adhering to the hydrophobic substrate. With a hydrophilic substrate, no ordered
deposition will occur until the first up-stroke because the hydrophobic tails are repelled by the
hydrophilic substrate as it is immersed in the water.

Therefore an even (2,4,6...) number of layers is always deposited onto a hydrophobic surface and
an odd (1,3,5...) number onto hydrophilic surfaces.

The surface quality and composition of the substrate controls the nature of subsequently deposited
layers. The deposition of the first layer is also of importance as this predetermines the manner in
which subsequent layers are laid down. For consistent film quality, the monolayer must be kept
at a constant pressure, even when transfer is actually occurring.

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Langmuir Blodgettry

Hydrophilic substrates
Deposition onto hydrophilic substrates proceeds in a similar manner, with the exception that the
first layer is not deposited until the first 'up' path, Figure 3.10.

This is a result of the water meniscus onto a hydrophilic surface being curved upwards and, when
the substrate is moved down into the subphase, the curvature of the meniscus and the direction
of motion do not coincide. Hence, molecules cannot be deposited.

Thus the first monolayer on a hydrophilic substrate is deposited on the first 'up' pass through the
monolayer, as the direction of the meniscus now favours the end of the molecule attracted to the
surface.

It is strongly recommended that, when using hydrophilic substrates, the substrate be immersed in
the subphase prior to spreading and compressing the monolayer. This will any prevent molecular
film aggregates depositing onto the hydrophilic surface during the first down stroke - these have
been observed to cause horizontal streaking - bands across the substrate perpendicular to the
dipping direction.

Figure 3.10: Wetting of a hydrophilic substrate and deposition of the first monolayer
onto a hydrophilic substrate

Transfer ratios & meniscus radius

An good measure of how well a film has transferred to a substrate is the transfer ratio, given by:

TR = area of monolayer removed from subphase at constant pressure

area of substrate immersed in water

Such a ratio is usually measured for each substrate pass through the air-water interface. However,
it must be remembered that the measured transfer ratio is an aggregate value over the entire
immersed surface and often requires interpretation. It is possible, for instance, to measure a TR
of 0% if 100% deposition takes place on one face of the substrate and 100% of film is peeled off
the other face.

It is important to realise that for every layer after the first layer, deposition does not take place until
the meniscus has 'flipped over', as shown in Figure 3.9 (previous page). This is a result of the fact
that the monolayer has to turn itself 'on its head' to continue the deposition of the second layer.
This gives rise to the 'head to head and tail to tail' structure of the amphiphilic Langmuir-Blodgett

30
 Langmuir Blodgettry

film, Figure 3.11. If the meniscus radius is not taken into account, then inaccuracies will occur in
the transfer ratio calculation. For instance, if the meniscus radius is 5mm and the length of the
sample is 50mm, then a 10% error would occur if the area calculation were made from the point
of substrate movement reversal, rather than from the point of the meniscus flipping over.

In the Nima software, the meniscus radius is taken into account in the transfer ratio calculation and
can be set in the Dipper Menu.

Deposition Types
Amphiphiles deposit in this 'head to head and tail to tail' (HHTT) fashion - on both the up and down
stroke of the substrate - resulting in 'Y-type' structures.

Y
Figure 3.11: Y-type deposition onto a hydrophilic substrate

There are two other deposition modes which have been observed - 'X' and 'Z' type. At present
there is no complete understanding of why some molecules dip in the X and Z manner, as this goes
contrary to the whole LB principle (although such phenomena can be very desirable in the field
of non-linear optics where such non-centrosymmetric structures are required). Films which
apparently deposit as X or Z-type have often been found to be Y-type after X-ray analysis. Poor
transfer ratios are not necessarily indicative of X or Z-type deposition but rather may simply imply
patchy film adhesion, the film consisting of small areas of Y-type deposition interspersed with
undefined regions where film may have been deposited and peeled off repeatedly. If 'X' or 'Z' type
deposition is observed, great care must be used when interpreting results and all cleaning methods
thoroughly reviewed.

X Z
Figure 3.12: 'X' and 'Z' type deposition

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Langmuir Blodgettry

Alternate layer deposition

The Nima alternate layer dipper allows the fabrication of multilayers containing 2 different film
forming materials.

By depositing and compressing two different materials in compartments 'A' and 'B' and
programming the dipper to pass down through monolayer A and up through monolayer B, a non-
centro-symmetric multilayer structure with the sequence ABABAB... can be produced.

Such structures have been used to produce pyroelectric Langmuir-Blodgett films, using a long
chain fatty acid as one material and a long chain amine as the other. Alternate monolayers have
also been observed to exhibit second-order non-linear optical effects. Organic materials with
large non-linear susceptibility coefficients which would normally stack in a centro-symmetric
manner are incorporated into a non-centro-symmetric structure by the use of passive spacer
monolayers such as fatty acids. To achieve the required structure, the spacer monolayers are
alternated with the active monolayers.

Figure 3.13: Alternate layer deposition

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 Langmuir Blodgettry

Laboratory Requirements

Safety
Before using any solvent, familiarise yourself with the relevant safety procedures. Solvents must
never be inhaled or touch your bare skin. Work in a fume cupboard when making up the solutions.
Similarly, when making up solutions of metal ions such as cadmium and potassium, always wash
your hands afterwards, to prevent accidental ingestion.

Check with your laboratory supervisor on safety regulations and correct disposal after
use. Remember you are responsible for your own and other's safety.

General
When studying mono-molecular layers which contain at most a few milligrams of material, even
a small amount of contaminant can cause serious errors.

The trough, substrates and other apparatus must be kept as clean as possible. Extraneous greasy
material concentrates at the air-water interface; the source of such contamination is usually grease
from fingers or hair, this being transferred to the subphase by supposedly clean instruments which
have been handled. Clean forceps or tweezers should always be used when handling substrates
and for all operations it is advisable to wear disposable, powder-free polythene gloves. It is
recommended that the syringes used for deposition are cleaned in between use and that they are
rinsed at least once with the solution to be deposited. Clean laboratory coats should be worn, not
only for protection but also to prevent the deposition of fibres from clothing onto the subphase.

When not in use the trough should be kept empty of water, covered and out of direct sunlight. If
being moved, the pressure sensors and dipper mechanism should be removed from the trough to
prevent accidental damage.

Lab environment
As with all aspects of Langmuir-Blodgettry, cleanliness is of the utmost importance. Airborne
particulates tend to accumulate at the water surface. To combat this, the water surface should be
cleaned thoroughly using the water suction pump and the trough should be situated in as clean and
dust-free environment as possible. When the trough is filled with water the clear covers should be
in place over the water surface and dipper mechanism to protect the trough from the vagaries of
the atmosphere.

Particular care must be taken with Langmuir-Blodgett films which are to be used for optical or
electronic applications, as dust particles can become incorporated into the films and give rise to
light scattering, pinhole defects and ambiguous results. Some troughs are housed in clean room
facilities which maintain a positive pressure and filter the air intake through micropore filters.
Surfaces are usually sealed and temperature and humidity are controlled. An isolated laminar flow
cabinet can also be used as an alternative. However, such facilities are not essential if care is taken
to operate the trough with regular cleaning in a relatively dust-free laboratory atmosphere. The

33
Langmuir Blodgettry

room in which the trough is situated must be adequately ventilated to ensure that solvent fumes do
not accumulate in dangerous quantities.

Excesses of temperature and humidity should be avoided, as should locating the trough in the close
proximity to vibrating machinery as such vibrations can cause premature collapse of monolayer
films. An anti-vibration table is useful if problems with obvious ripples from external disturbances
can be discerned. However, small vibrations do not appear to cause serious problems and have
been known to enhance film quality by annealing the surface monolayer.

Trough
The Nima troughs are fabricated from Polytetrafluoroethylene (PTFE), a material which will not
contaminate the subphase. The polymer is essentially chemically inert, will not leach plasticiser and
is the most hydrophobic polymer known. PTFE can be subjected to very rigorous cleaning
procedures.

In general, the best way to keep the trough clean is to use it regularly and to avoid unnecessary
collapse of mono-molecular films. The tissues used to wipe the trough must be surfactant-free,
such as the 'Kimwipes' supplied (type 7105, available from Kimberly-Clarke). Some other
tissues, even if they are 'guaranteed 100% clean' may contain amphiphiles that prevent formation
of pure monolayers, as 'cleanliness' has a different meaning in different environments. For example
the Kimwipes would be disastrous in a semi-conductor fabrication area, as they produce clouds
of dust particles, but they are ideal for LB films as they are surfactant free.

Before and after use, the trough should be thoroughly cleaned. Any leftover monolayer material
should be removed from the subphase surface before the trough is emptied. To ensure that all parts
of the trough are cleaned, the dipping head and barriers should be removed from the main part
of the trough first. The barriers can be removed and wiped with a solvent laden tissue.

Organic solvents are the best available degreasing agents and will work over a wide range of
solubilities and a thorough wipe with a chloroform laden Kimwipe cleans the PTFE well. Care
must be taken to wipe off all excess chloroform, as pools of CHCl3 will evaporate leaving
surfactants behind. Take great care not inhale any chloroform and always wear gloves. If
your lab supervisor forbids the use of chloroform, use isopropyl alcohol instead.

To clean off more hydrophilic surfactants, we recommend making up a solution of potassium

octanoate which is a very mild detergent. First the trough is rinsed out with this and then thoroughly
rinsed with pure water. The full procedure is given in our website at:

www.nima.co.uk/advanced/cleanliness

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 Langmuir Blodgettry

Chemicals
The materials which are deposited should be as pure as possible. Very small quantities of
impurities, especially surface active contaminants, can radically alter the molecular area calculated
from the isotherm and affect the material’s film forming characteristics.

To avoid contamination, and so improve results, impurities should be restricted during synthesis.
Care should not only be taken with the purification of materials but also with the solvents and
starting materials used, which should be of the highest available purity.

Once prepared, materials should be carefully stored and handled to prevent hydrolysis, oxidation
or contamination. Ideally, samples should be kept in a clean, dry, sealable, inert vessel, preferably
made of glass as there can be contamination from plasticisers in plastic materials. Non-
contaminating methods should be devised for the weighing out and transfer of materials. Care
should be taken to ensure that spatulas are kept clean.

Water
The Nima troughs have different capacities between 40 and 1500ml. This small volume reduces
the demand of deionised water and the risk of contamination, and also eases cleaning.

The water used in a Langmuir-Blodgett trough should be as pure as is possible. The quantity of
particles, ions, and surface-active materials should be kept to such a low level that they will not
significantly affect the surface properties of monolayer systems.

In the past, water was usually distilled a number of times, sometimes with an oxidative stage using
an alkaline permanganate solution. Nowadays, reverse osmosis, ultra-filtration, and ion exchange
resins are commonly used. A charcoal filter is usually located on the feed line to the still. For
consistent results any of the commercially available deionisers are recommended. (Manufacturers
include Barnsted, Elga, Millipore & others.)

The water should be freshly made and discarded every time the molecule type is changed. Storage
should be in clean vessels which are inert; some plastic containers leach dialkyl phtalate esters
which are used as plasticisers in their manufacture.

The prime criterion for establishing the cleanliness of the subphase is a high value of surface tension.
The surface tension of pure, clean water at 293K is 72.8mN/m. A minimal change should be
observed on aging and insignificant changes should be seen on compression of the surface. It
should be noted that the value will decrease with an increase in temperature. The surface tension
of the water in the trough can easily be measured by lifting the Wilhelmy plate out of the water after
having zeroed the pressure sensor. To protect the water surface from air borne particulates the
transparent lid should be kept on the trough whenever possible when the trough is full of water.

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Langmuir Blodgettry

Solvents
Some Langmuir-film forming materials, such as vegetable oils, spread spontaneously on a water
surface. However most materials must be deposited onto the subphase in a solution of a volatile
solvent. The solvent which is chosen is critical and will affect the film forming properties of the
solute. A number of factors must be considered:

Firstly a solvent must be chosen which has sufficient solvent power to dissolve a substantial
quantity of the material under investigation. A solution with much less than 0.1 mg/ml will require
too large a volume to be deposited to form a reasonable area of compressed monolayer.

The solvent must also be chemically inert with respect to the material under study and should also
be relatively pure. Small amounts of contaminants such as grease can be removed by distilling the
solvent in grease-free glass systems. The cleanliness of the solvent can be verified by spreading
the solvent neat on the subphase, allowing it to evaporate and then running an isotherm of the
remaining surface material. Any increase in surface pressure observed will be due to surface active
contaminants in the solvent which need to be removed. This technique is known as 'blank
spreading' and, as many commercially available solvents contain film forming contaminants, is
highly recommended.

The volatility of the solvent must also be considered - it must be such that the evaporation time
is short but not so short that the concentration of the solution cannot be determined due to
evaporation. The boiling point of the solvent should lie in the range 40-80oC. Important factors
to consider are the hazards associated with organic solvents - when allowing the solvent to
evaporate the solvent vapours should not be inhaled.

Organic solvents which are very soluble in water should be avoided as they will tend to carry
amphiphilic material into the subphase and precipitate it out. If a water-miscible solvent is used,
a high concentration of the material to be studied must be used to counteract the effect of the
material being pulled into the subphase. Care must be taken when interpreting molecular areas
obtained with such solvents as they will usually be incorrect. If a material is not soluble in non-polar,
volatile spreading solvents, an acetone-hydrocarbon (e.g. hexane) mixture can be used to increase
the amount of solute which will dissolve without introducing serious solubility problems.

The table below shows the properties of a few solvents which have been used for depositing
Langmuir film forming materials. Solubilities in water are at 25°C, in g/Kg.

Solvent Melting point Boiling point solubility in

(°C) (°C) water
n hexane -94 69 0.01
Cyclohexane 6.5 81 0.07
Choloform -64 61 8
Diethyl ether -116 35 75
Acetone -93.4 56 ∞
Dichloromethane -98 40 1.3

Table 3.3: Properties of solvents

36
 Langmuir Blodgettry

Substrate
The quality of the first layer deposited onto the substrate determines the deposition behaviour of
subsequent layers - defects in the first layer can be passed through to and observed in layers
subsequently deposited. Because the substrate determines the nature of the first layer
deposited, it must be thoroughly cleaned.

At all stages of the cleaning procedure care should be taken not to touch the slides with fingers
as the skin grease contains a mixture of surface active biological lipids.

Substrates can be divided into two groups according to their surface - they can be either
hydrophilic or hydrophobic. A standard glass microscope slide or a polished silicon wafer make
excellent substrates for deposition of LB films. Both are normally hydrophilic, the silicon always
has an oxide layer after exposure to air.

Many substrate cleaning procedures are commonly employed. One which has been found to work
well is to wash the slides with detergent, then rinse in an ultrasonic bath in deionised water and then
with isopropanol. Instead of using an ultrasonic bath, Soxhlet cleaning can be used. Argon plasma
cleaning (100W incident power at 13.6MHz and 0.1 Torr for 2 minutes) just prior to deposition
also gives an excellent surface.

Strong oxidising agents such as acidic peroxide or chromic acid are not recommended - as they
are a health hazard and require the substrate to be thoroughly rinsed post immersion because they
can introduce as many contaminants as they remove.

A hydrophilic glass surface can be prepared by soaking the clean slides overnight in a 2g/dm3
solution of sodium hydroxide. They are then rinsed with ultra-pure water and dried in a stream of
dry nitrogen.

A hydrophobic surface is obtained by standing the clean glass slide overnight in a fume cupboard,
in a beaker containing a few drops of hexamethyl disilazane and covered with a watchglass. On
evaporation, the hexamethyl disilazane condenses onto the clean slide, rendering it hydrophobic.
Evaporation of gold will also make a slide hydrophobic. Katherine Blodgett also used the
technique of rubbing in molten ferric stearate (see the 'Tutorial' section) which works well and is
not as hazardous to health as the other techniques.

Glass is not the only material which can be use as a substrate. Many other surfaces such as fused
silica and silicon wafers can also be used. When infra-red studies of Langmuir-Blodgett multilayers
are to be undertaken, calcium fluoride plates which are effectively insoluble in water and
transparent to infra-red radiation can be used. All these materials can be prepared in the same
manner as glass.

After preparation the slides should be stored in a clean dust-free sealable box.

37
Langmuir Blodgettry

Bibliography
This section contains a review of a number of books, journals and conference proceedings as a
guide to locating detailed information on the history, practicalities and current research in the field
of Langmuir-Blodgettry.

The list of references from books and journals to be found in this section is by no means
comprehensive as the amount of available literature in the field of Langmuir-Blodgettry is
constantly and rapidly growing. It is included merely as a starting point for those beginning to work
with Langmuir and Langmuir-Blodgett films.

Books
The behaviour of monolayers and the chemistry of surfaces is well documented in:

Rideal E.K. and Davies J.T., ‘Interfacial phenomena’; 2nd Ed.; Academic Press, 1961.
Shaw. D.J., ‘Introduction to colloid and surface science’, 3rd Ed.; Butterworths London, 1980.

Monolayer properties and built-up multilayers are considered in the slightly dated but
comprehensive and excellent text:

Gaines G.L. Jr., ‘Insoluble monolayers at gas liquid interfaces’; Interscience New York,
1966.

Reviews of the theory and practical considerations concerning the formation of Langmuir-
Blodgett films can be found in:

Roberts G.G. (Ed.), ‘Langmuir-Blodgett films’; Plenum Press New York, 1990.

Ulman, A., 'Ultrathin organic films', Academic Press, Boston, 1991.

Ashwell G.J. (Ed.) ‘Molecular electronics’, chapter by Peterson I.R.; Research Studies
Press, 1992.

Tredgold, R.H., 'Order in thin organic films', Cambridge University Press, 1994.

References
The journal, ‘Thin Solid Films’ regularly features contributions on Langmuir-Blodgett
and related films and several volumes have been devoted exclusively to Langmuir-Blodgett
films. All are available from, Elsevier Sequoia SA, Lausanne, Switzerland.

Special editions of ‘Thin Solid Films’ on LB films:

Barlow W.A. (Ed.), 1980, Vol 68.

Roberts G.G. (Ed.), First international conference on LB, Durham, England; 1983, Vol 99.

Gaines G.L. Jr. (Ed.), Second international conference on LB, Schenectady, USA; 1985, Vols
132, 133 and 134.

38
 Langmuir Blodgettry

Stroeve, P. and Franses (Eds.), Molecular engineering workshop, Davis, USA; 1987, Vol 152.

Möbius D., Barraud A. and Roberts G.G. (Eds.), Third international conference on LB,
Göttingen, Germany; 1988, Vols 159 and 160.

Fukuda K. and Sugi M. (Ed.), Fourth international conference on LB, Tsukuba, Japan;
1989, Vol 180.

Barraud A. (Ed), Fifth international conference on LB, Paris, France; 1991, Vols 210 and
211

In recent years, 'Langmuir' appears to have superseded Thin Solid Films as the main
forum for LB work. It is published by the American Chemical Society.

Other journals
In addition to the above journals, the Journal of Colloid and Interface Science, the Journal
of Molecular Electronics (up to Dec 1991 Vol 7, No 3.), Advanced Materials for Optics
and Electronics (From Jan 1992) provide good background reading.

The Journal de Chemie Physique published a special issue relating to Langmuir-Blodgett

films in 1988. This issue includes Langmuir -Blodgett film work in the fields of biology,
non-linear optics and molecular electronics amongst others.

Barraud A. (Director), ‘The NATO Advanced Workshop on Langmuir-Blodgett films and

related structures’; Journal de Chemie Physique, 1988, Vol 85.

Historical
Benjamin Franklin’s initial communication to the Royal Society of London in 1774
contains details of his original monolayer experiments on the pond at Clapham and also
describes the interesting effects of monolayer films on supposedly dead flies!
Franklin B., ‘Of the stilling of waves by means of oil’; Philosophical Transactions of the
Royal Society, 1774, Vol 64, p 445.

Wilhelmy first described the measurement of surface tension in:

L.Wilhelmy, Angew. Physik, vol 119, p177 (1863)

Agnes Pockels' original letter to Lord Rayleigh was published in:

A.Pockels, Letter to the Editor, Nature vol 43, p437, 1891.

A paper by Katherine Blodgett describes one of the first suggested practical and
commercial applications of Langmuir-Blodgett films, as anti-reflection coatings on glass
(part of the work from which is repeated in the ‘Tutorial’ section):
Blodgett K.B., ‘Use of interference to extinguish reflection of light from glass’; Physical
Review, 1939, Vol 55, pg 391.

A brief history of Langmuir-Blodgett films, containing many of the references to the

original work on Langmuir and Langmuir-Blodgett films can be found in the preface to
Volume 99 of Thin Solid Films:
Gaines G.L. Jr., ‘On the history of Langmuir-Blodgett films’; Thin Solid Films, 1983, Vol 99,
pg ix.
39
Langmuir Blodgettry

Interest was rekindled in Langmuir films by the elegant work of Kuhn & Möbius:
Kuhn,H. and Möbius,D., 'Systems of mono-molecular layers - assembling and physico-chemical
behaviour', Angewandte Chemie (Int'l Ed) vol 10, 1971, No 8, p 629.

Reviews
Reviews of Langmuir-Blodgett film practice and applications and possible directions for
the future of Langmuir-Blodgett films in molecular electronics include:

Roberts G.G. ‘An applied science perspective of Langmuir Blodgett films’; Advances in
Physics, 1985, Vol 34, pg 475.

Peterson I.R., ‘Langmuir-Blodgett films: Structure and application’; Journal of Molecular

Electronics, 1987, Vol 3, pg 103.

Sugi M., ‘Langmuir-Blodgett films - a course towards molecular electronics: A review’;

Journal of Molecular Electronics, 1985, Vol 1, pg 3.

Roberts G.G., ‘Molecular electronics using Langmuir-Blodgett films’; Advances in Chem-

istry Series, 1988, Vol 218, pg 225.

Peterson I.R., ‘Langmuir-Blodgett films’; Journal of Physics. D. Applied Physics, 1990,

Vol 23, pg 379.

Swalen J.D., ‘Molecular Films’; Annual Reviews in Materials Science, 1991, Vol 21,pg 373.

Practical considerations
Details of practical considerations for the production and study of Langmuir-Blodgett
films can be found in

Mingins J. and Owens N.F., ‘Experimental considerations in insoluble spread monolayers’;

Thin Solid Films, 1987, Vol 152, pg 9.

Peterson I.R., Veale G. and Montgomery C.M., ‘Preparation of oleophilic surfaces for LB
deposition’; Journal of Colloid and Interface Science, 1986, Vol 109, pg 527.

Pethica B.A., ‘Experimental criteria for monolayer studies in relation to the formation of
Langmuir-Blodgett multilayers’;Thin Solid Films, 1987, Vol 152, pg 3.

Film characterisation
A comprehensive account of methods which can be used to characterise the structures of
Langmuir-Blodgett films once they have been deposited on a substrate is contained in the
fourth volume of the Journal of Molecular Electronics:

Vandevyver M. and Barraud A., ‘Methods of characterisation for Langmuir-Blodgett

films’; Journal of Molecular Electronics, 1988, Vol 4, pg 207.

Throughout this manual, data is quoted from:

Tennent R.M (Ed.), 'Science Data Book'; Oliver &Boyd, 1971.

40
TUTORIAL
Tutorial

Introduction
This tutorial is designed to teach you the basic commands of the Nima trough and the essentials
of Langmuir-Blodgettry by leading you through a series of examples. It is a good idea to read the
'Langmuir-Blodgettry' chapter first. You will repeat work done originally by Katharine Blodgett
in 1938* and prepare a multilayer film of zinc arachidate which is then skeletonised to display a
series of interference colours. This technique was originally used to prepare anti-reflection
coatings for glass.

Follow the instructions given. The buttons to click are shown in the left hand column;
additional comments are shown in italics. If you get stuck, stop whatever is going on by clicking
on the STOP button. To see a short description, right hand click on an item. For more detailed
explanations of the functioning of the trough software, please refer to the 'Software' chapter of this
manual.

Requirements

Before you begin, you will need:

. 1mg of arachidic acid to make into a monolayer

. About 100g of ferric stearate to make the substrate surface hydrophobic
. Glass slide (substrate) to deposit monolayers onto
. About 100mg of Zinc sulphate for the subphase
. Ethanol for skeletonising the LB film
. Chloroform for trough cleaning
. Ultra-pure deionised (DI) water for trough
. Kimwipe tissues (or similar surfactant free) for cleaning

Preparations
Solutions
You will deposit a mixture of arachidic acid and zinc arachidate onto your substrate. The zinc
arachidate is formed on the water when the arachidic acid is spread on a Zinc sulphate
subphase. The zinc ions bind to the (partly dissociated) arachidic acid and form zinc arachidate.
By chance, dissolved atmospheric carbon dioxide gives rise to the required pH 5.5, at which about
50% of the fatty acid is dissociated. The water used must be free from other contaminating metal
ions.

* 'Use of interference to extinguish reflection of light from glass', K.B.Blodgett, Physical Review,
volume 55, (1939) page 391.

42
 Tutorial

Make up a solution of approximately 1mg/ml of arachidic acid in chloroform and note

down the exact concentration. A total volume of about 100µl of solution will be needed,
but it is recommended to make up 10ml for future use. Store this below 10°C to reduce
evaporation. Use the glass bottle provided in the Monolayer Kit to minimise contamination
from surfactants.

- Make up a solution of about 10-4 M Zinc sulphate in deionised water in a clean container
- this can be made of borosilicate glass, as long as solution is not stored in it overnight,
as detectable quantities of mineral ions leach out of the glass after about half an hour.
Make up about 2 litres of solution so that the subphase can be topped up from time to time.
The molecular weight of Zinc sulphate (hydrated) is 287.5; 57.5mg will be needed to make
up 2 litres of 10-4 M solution.

Trough
- Wipe over the trough surface, with a 'Kimwipe' (type 7105, supplied with the trough
- or type EX-L No 34256 in the USA) soaked in chloroform wearing the polythene
gloves (also supplied). Make sure you are working in a well ventilated room and ask
your laboratory supervisor about safety regulations and toxic solvents.

- Wipe the other trough components (dipper mechanism, pressure sensor, acrylic trough
cover) with a Kimwipe soaked in alcohol to remove loose dust. Do NOT use chloroform
on plastics other than PTFE as it will dissolve them!

- Clean the syringe by sucking up and expelling a little solvent several times.

- Fill the trough with deionised water until it just brims over the top - about 2mm over
the rim of the trough.

Substrate
- Acquire a standard microscope glass slide.

- Clean the substrate initially by rubbing it vigorously with a cloth soaked in alcohol. Rinse
thoroughly with deionised water. Ultrasonic in deionised water.

- If a plasma etch unit is available expose the substrate to 2 minutes of Argon ion plasma
at about 0.1 Torr and 100W incident radiated power.

- Make the substrate surface hydrophobic by rubbing it with ferric stearate on a piece of
Kimwipe tissue until no visible trace of the chemical remains. Ensure that the no part of
the surface is missed.
A small quantity of ferric stearate is provided in your Monolayer Kit - more can
be synthesised or acquired commercially - please see the Technical Appendix.

43
Tutorial

Producing an isotherm
It is now time to run the software and turn the interface ON. Therefore, click on your trough icon,
or, if it is not your desktop, click on the Nima516.exe file in c:\Nima (or whichever directory you
have nstalled it into). The main screen of the software is illustrated below.

In order to produce an isotherm, the water subphase must first be clean. The molecules have to
be spread on the surface and the solvent is left to evaporate. They are then slowly compressed
and the resulting pressure-area isotherm displayed.

The following sections will lead you through this operation one step at a time. The software
commands are printed in bold down the left margin with an adjacent explanatory paragraph.
Additional comments are printed in italics.

In case of emergencies, click on the STOP button or hit the Esc key!

Figure 3.1: Main Screen of Nima Software

44
 Tutorial

Subphase cleaning
Ensure that the trough has been cleaned and filled with pure DI water.
Attach a paper Wilhelmy plate to the pressure sensor with the 'S' shaped hooks provided
and lower it into the water, so that about 2mm of it is immersed.

O Open the barrier(s) by clicking on the 'O' button.

Z Zero the pressure sensor.

Check that a reading of about 70 mN/m is obtained when the Wilhelmy plate is lifted out
of the water. If it does not, check the change in surface pressure for the 100mg calibration
weight by adding the calibration pan and then the weight. This change should be 46.7mN/
m. If it does not, recalibrate the pressure sensor as described in the 'Software' section.
The reading may drift initially, this is because the paper plate is still absorbing water.

Barrier Set the barrier speed to 100 cm²/min by entering '100' in the 'Barrier Speed' box.
Speed To save time, you can set it to larger values, say 250, or even 500 for larger troughs.
100

Barrier Select 'Isotherm' from the 'Barrier' dialog box to start the isotherm. The barrier will
Isotherm move at the given speed until either the space bar is pressed or the barrier travels
outside its 'allowed' position (this is set in the Monolayer Menu and prevents accidental
damage to the trough.)

Examine the isotherm produced. It should be almost flat except for a slight 'tail'at small
areas due to the presence of dirt on the water surface.

Turn on the aspirator pump and touch the pipette to the water surface to suck off any
floating material, such as dust and amphiphilic contaminants. If the pipette end is positioned
correctly, there will be a louder sucking noise as air is sucked up withwater. Move the
head of the pipette around to collect all the material and clean for about 30 seconds.

O Open the barrier(s) by clicking on 'O' .

Z Re-zero the pressure sensor.

This is necessary because the water level in the trough has now changed. Make sure that
the lower edge of the Wilhelmy plate is still touching the water surface.

Keep cleaning until the isotherm produced is completely flat. The change in surface
pressure on compression should be less than 0.5mN/m. For a quicker check on
cleanliness, simply close the barriers ('C') and watch the change in pressure sensor
reading.

If you have sucked off too much water, please refill the trough until the level is again
about 2mm above the rim of the PTFE. When refilling, always add the water behind
the barrier i.e. the other side from where the monolayer is to be spread. This will ensure
that any surfactants present in the water will rise to the surface in the unused compart
ment behind the barrier. Of course, the water should be clean, but you can't be too
careful in LB films!

45
Tutorial

Monolayer Menu

Figure 3.2: Monolayer Menu

To ensure that the area axis (in A² / molecule) is calibrated correctly, go to the Monolayer Menu
and enter the correct molecular weight, concentration and volume of your solution.

Barrier Select 'Monolayer Menu' from the 'Barrier' menu.

Mono Menu

MW Enter the molecular weight of your molecule.

Conc Enter the concentration of your solution.

Vol Enter the volume of your solution in µl.

The other variables can be left for now. They are fully explained in the 'Software'
chapter.

46
 Tutorial

Spreading
Now that the conditions have been set, the molecules can be spread on the subphase.

- Rinse out the syringe by drawing up and expelling a little chloroform. Make sure that you
always expell excess chloroform into a designated 'chlorinated waste' bottle.
- Draw up 50µl of the arachidic acid solution into the syringe and deposit it drop by drop
onto the water from just above the surface.
There is no need to deposit on different places on the trough when using arachidic
acid - the molecules will spread out to cover the complete area available. With other
molecules, particularly those with large dipole moments, this may not be the case
and 'islands' can form.
- Leave the solvent to evaporate.
All the solvent must evaporate but Katherine Blodgett found that if it was given too
long, the deposited films were 'streaky'. The evaporation time does appear to have
some bearing on film quality - you may wish to devote your PhD to investigate this
unexplained observation! However, just wait until the pressure reading returns to
zero - that will do for now.

Compression
Barrier Set the barrier speed to 100 cm²/min by entering '100' in the 'Barrier Speed' box.
Speed This is a reasonable compromise between a good isotherm (i.e. undistorted by
100 dynamic effects) and time available. At this speed, the barrier takes about 5 minutes
to close for a standard size trough.

CLEAR Clear the memory and the graphs by clicking on 'CLEAR'. You will be asked to
confirm this clear, as once cleared, all the data is irretrievably lost!
This will clear the data stored when the subphase was being cleaned. It is good
practice to clear the data before taking an isotherm, to prevent the graph getting
cluttered up with unnecessary data from previous runs.
Graph Switch the area axis between absolute area (cm²) and area per-molecule (Ų) as
cm²<>A² calculated from the data in the Monolayer Menu.

Barrier Start the compression by clicking on 'Isotherm' in the 'Barrier' menu.

Isotherm Watch the isotherm on the screen and compare it to Figure 3.3. It should show three
distinct regions - an initial flat region, corresponding to a 'gaseous' phase of the
molecules on the water, a gently rising liquid-expanded or 'liquid' phase and a
steeply rising, liquid-condensed or 'solid' phase.

STOP When the isotherm begins to collapse, click on STOP to stop the compression.
At this point, the steep upward rise of pressure will begin level off.
Physically, the monolayer can no longer support the force applied and the
molecules move over each other to form aggregates on the surface, or are
dissolved in the subphase. With highly coloured films, this is clearly visible.
Remember that a surface pressure of 50mN/m is equivalent to 200 atmospheres
pressure over the molecular length of 25Å !

47
Tutorial

Barrier Change the barrier speed to -100 cm²/min. A negative speed corresponds to the barrier
Speed moving backwards.
-100

Barrier Expand the floating monolayer by clicking on 'Isotherm' again.

Isotherm The isotherm should have exactly the same shape as when the film was compressed
but will be shifted towards smaller areas (i.e. to the left of the graph) by an amount
equal to the area of collapsed film.

Barrier Clean off the surface.

Pi control Use the suction pump with its teflon tip to clean the molecules off the surface as previously
described.

Target Select 'Target Pressure' from the 'Variables' menu and adjust it to 25mN/m.
Pressure This will compress the barriers, keeping the pressure at 25mN/m as you remove the
25 molecules, ensuring that the monolayer is not collapsed. Cleaning shouldn’t take
more than a minute or so.

Well done - you have now taken your first pressure-area isotherm!

Figure 3.3: Typical isotherm of fatty acid

Saving and further analysis

File Save the isotherm, by clicking on 'Save' in the 'File' dialog box.
Save Enter a name (such as 'test1') and the data will be saved as a *.txt file (i.e. test1.txt)
along with its operating conditions which are saved as a *.con file. The data file
can be loaded into Excel (or other spreadsheets) and the data will be displayed in
columns, each headed by a label to signify what it is. It can be charted and pasted
into your reports or papers.

Graph Click on 'P&A-Time' on the 'Graph' menu to view two separate plots of pressure-time
P&A-T and area-time.
48
 Tutorial

Graph Click on 'Graph' and 'Change Axes A²<>cm²' to convert the area scale to Ų. The
A²<>cm² conversion will use the data supplied by you in the Monolayer Menu.

Right click over the graph and de-select 'AutoScale X' - then use the pointer to mark off
an area of the isotherm such as the 'liquid condensed phase'. The selected area will expand
to fill the screen and the Area/molecule / Ų will be displayed in the box below the graph,
Figure 3.4.

If you disable auto-scaling for both X and Y axes, then you can set the scaling of the axes
by writing over theminimum and maximum abscissa values. Or you can select different
areas of the graph with the 'X-Y scaling palette. Feel free to experiment.

Cursor Click on the cursor control palette (bottom left of the graph).
control There is a white square which activates the cursor controls when clicked. You can
move the cursor anywhere on the screen and read off the X and Y co-ordinates. Click
on the little padlock icon and select 'lock on plot' to move the cursor along the
actual curve.

(a) (b)

Figure 3.4: Isotherm of fatty acid

a) x-axis now in Ų/molecule - liquid condensed phase selected
b) expanded to read off 'zero pressure molecular area'

Further investigations

Repeat the isotherm procedure two or three times, varying the amount of material used, solvent
evaporation time, compression speed etc. to try to improve upon your first isotherm and get a feel
for the technique.

You might like also to change the concentration of Zinc sulphate in the subphase. This will alter
the pressure at which the liquid-expanded changes to the liquid-condensed phase. The greater the
concentration of ZnSO4 , the lower the pressure of the phase change. The liquid expanded phase
disappearing altogether at about 10-3M concentration.

49
Tutorial

Depositing a multilayer LB film

Now that you have an isotherm of the material to be studied, it can be deposited with some
confidence. Arachidic acid / Zinc arachidate forms good, optical quality Langmuir films on the
subphase and deposits easily at surface pressures of about 25mN/m (in the liquid condensed
phase).

For simplicity, the following sequence is for a conventional LB dipper:

- Prepare a subphase of about 10-4M ZnSO4 .

- Clean and check the water surface as before.
- Have the glass slide coated with ferric stearate ready.

U Move the dipper to its topmost position by clicking on 'U'.

Attach the glass slide to the clamp.

D Move the dipper down by clicking on 'D' until the lower edge of the slide is about
5mm above the water surface.

STOP Stop it by clicking on STOP

h Read off the dipper position reading - let's call this h mm.
Select 'Dip Top End' from the 'Variables' Menu (top right of screen) and enter h into the
box (top left of the screen).
The 'Variables' Menu contains a number of useful parameters that may be changed
in the main screen of the program before or during a run. Hence, it is not necessary
to stop the process and go to the Monolayer or Dipper Menu in the middle of a run.

h+d Now decide how far you want to dip the substrate into the water - i.e. what length of
substrate you want to coat. Typically this may be 30mm for a standard dipper or maybe
10mm if you are using a mini dipper with a small slide.
If we call the immersion depth 'd', then enter 'h+d' into the 'Dip Bottom End' variable
box (again selected from the 'Variables' Menu).

Z Zero the pressure sensor by clicking on 'Z' .

Then spread the solution of molecules onto the subphase.
To avoid having to replenish the molecules on the subphase too often, it is useful to put
the maximum possible number on each time. Spread the solution with the syringe until the
surface pressure displayed in the data margin to the left of the axes just begins to rise. At
this point, the surface is completely covered with molecules.

Target Select 'Target Pressure' from the 'Variables' Menu (top left of screen)
pressure Enter a target pressure of about 25mN/m in the 'Target Pressure' box.
25 The exact value will depend on the phase change between 'liquid expanded' and
'liquid condensed' phases. It is best to deposit just 2 or 3 mN/m above the phase
change, as the molecules will be tightly compressed, but small excursions in
pressure (caused by the action of the slide entering the water) will not give rise to
local collapse of the monolayer.

50
 Tutorial

Barrier Enable the pressure control by clicking on 'Pressure Control' in the 'Barrier' menu.
Pi Control The barrier(s) will compress the monolayer to the target pressure according to
the relationship:
barrier speed = δπ * (feedback gain)

whereδπ is the difference between current pressure and target pressure and
feedback gain is a numerical value (also set in the 'Variables' Menu). Larger values
of gain increase the barrier speed and so reach the target pressure more quickly, but
may then overshoot. Too low a value means that target pressure is never achieved.
A critical value of 1.0 is recommended.

The barriers will slow down as the target pressure is reached. Wait until surface
pressure is within 1mN/m of its target.

Note that the maximum barrier speed under pressure control is limited by the value
given in the 'barrier speed' display box (at the centre left of the screen). This is useful
if you are using delicate molecules and don't want to compress them too fast.

Dipper Begin dipping.

Progrm Dip The dipper will move down through the water surface.
As the slide moves through the interface, the monolayer is transferred onto the solid
surface. The barriers will move inwards to maintain the target pressure automatically.

Graph Select the 'Dipper-Area' graph from the 'Graph' dialog box.
Dip-Area A series of straight 'V' shaped lines will appear as the dipper is moved up and down and
the barrier moves in to compensate for removal of molecules from the water surface.

Layers Adjust the 'Layer Required' box to 40, so that 40 layers (equivalent to a thickness of
Req 40 λ /2 are built up, as explained later under 'skeletonisation').

The dipper will continue to deposit layers on to the substrate until either all 40 layers have been
deposited or the area of monolayer is reduced to below the following:
area < [ ('close-to' area + 2 * substrate area)]
You are then requested by the software to reopen the barriers and respread the molecules.
Spread the material, as before. If you have not collapsed the film, there is no need to clean the
surface, Then re-compress and restart the dipper.
Continue until all 40 layers have been deposited.

Points to consider during dipping

* Do not stop the dipping whilst a layer is in the process of being transferred - it will
reduce the quality of your LB film.

* Do not clear the memory whilst dipping as this will clear the record of the number of
layers. You can, of course, keep a separate tally, if you want to work with a clear screen
after every re-spreading.

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Tutorial

* Watch the meniscus of the subphase as deposition is occurring.

If the meniscus is uniform, the deposition likely to be is good; if it 'dances around', the
deposition is unlikely to be as good. This 'dancing' indicates imperfections on the substrate
surface.
* The dipping speed, target pressure, feedback gain and 'end' positions can all be varied as
the dipping is taking place, without stopping the program. The 'Variables' Menu allows
selection of the appropriate variable and the preset values are altered using the 'up' and
'down' arrows next to the box.

Completion
Once all the layers have been deposited, the substrate can be removed and the data can be
saved and plotted out. A typical deposition isotherm is displayed below.

* Save the data ('File' dialog box and 'Save' with a user defined file name).

* Remove the substrate with its deposited Langmuir-Blodgett film. Be careful not to touch
the surface.

* Store it in a cool, dry place.

* Clean the remaining monolayer off the subphase surface.

* Empty the trough.

* Clean the syringe.

* It is recommended to always empty the trough overnight. If you prefer to leave the trough
full of water to prevent dirt falling on the PTFE surface, please remove dipper and pressure
sensor(s) to prevent corrosion of electronic components.

Figure 3.5: Typical deposition pressure-area isotherm

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 Tutorial

Further analysis
Graph Click on 'P&A-Time' on the 'Graph' menu to view two separate plots of pressure-time
P&A-T and area-time. This will show the 'steps' in area as the barrier is moved in to compensate
for the removal of monolayer onto the substrate, Figure 3.6 below.

Figure 3.6: Typical deposition (pressure & area) - time isotherm

Graph Click on 'Diper-Area' on the 'Graph' menu to view the plot of area against dipper position
Dipper If there was good deposition, this plot will be in a series or regular 'V' s. As the dipper
-Area is oscillated up and down regularly, the barrier moves in linearly to compensate for the
removal of monolayer, Figure 3.7 below.
Note that it takes a few mm worth of dipper travel at the start of every layer before
deposition recommences - this is caused by the reversal of the meniscus radius, as
explained previously in the 'Langmuir-Blodgettry' chapter of this manual.

Figure 3.7: Typical dipper position-area isotherm

53
Tutorial

Transfer Click on 'Transfer ratio' on the 'Graph' menu to view the plot of transfer ratios (TRs).
Ratio Ideally, TR is always 100%, but rarely in practice! There are many reasons for this, as
explained in 'interpreting transfer ratios' overleaf.

Figure 3.8: Typical transfer ratio plot

Skeletonisation to produce an anti-reflective (AR) coating

It is now time to 'skeletonise' the multilayer you have produced. Before skeletonisation, the films
refractive index is very similar to that of the substrate (about 1.50) making it almost invisible. The
film is skeletonised by dissolving away the arachidic acid, leaving only the zinc arachidate. This
reduces its refractive index and brings the film’s optical thickness close to one quarter wavelength
for blue light.

- Pour enough ethanol to cover the LB film into a beaker.

- Immerse the film in the ethanol for a number of seconds.

The exact time required varies between ten seconds and two minutes. When the film is first
immersed, it loses arachidic acid fairly quickly but the rate then slows. Remove the film
slowly to allow time for the surface to shed the alcohol.

- The colour becomes more vivid and shifts towards the red with longer soaking as the film’s
refractive decreases towards the extinction value, n = √nglass.

- Hold the dried slide in the reflection of a lamp. You will be amazed by the quality of the
AR coating!

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 Tutorial

Deposition onto hydrophilic substrates

The previous section dealt with deposition onto an hydrophobic substrate - that is to say the
first layer was deposited on the 'down' path. Deposition can just as easily take place onto an
hydrophilic substrate. The only difference is that the first layer is on the first 'up' path. Hence
the substrate must first be lowered into the water.

It is recommended that the substrate is lowered into the water prior to spreading and compressing
the monolayer, as otherwise some irregular deposition may take place onto the hydrophilic
substrate as it is immersed through a compressed monolayer.

The software can be used to start the deposition below the water surface. This is done by 'fooling'
the computer that the first layer has already been completed. Hence the number of layers set will
actually be (n + 1) where n is the actual number of layers to be deposited. Thus even if only one
layer is required, 2 layers must still be entered in the 'Layers Required' box.

The following sequence should be followed for deposition onto an hydrophilic substrate:

Dipper Enter the Dipper Menu and set the dipping routine but remember that your first
Menu layer will be the second layer as far as the computer is concerned. Thus enter (n+1)
layers. Set the 'top' and 'bottom' positions for the substrate, as explained in 'Setting
the Dipping Conditions' earlier in this chapter.
C Close the barrier(s) and clean the surface.
O Open the barrier(s).
Then attach the substrate to the dipper and, still with the barrier(s) open, move the
dipper so that the substrate is immersed:
D Move the dipper down.

STOP Click on STOP to stop the dipper at the correct position.

Then spread and compress the monolayer in the usual way:

Barrier Start the compression under pressure control.

Pi Control

Dipper When the film has reached its target pressure, click on 'Program Dip' to start the dipper.
Progrm Dip As the dipper is already below the surface of the water, it will assume that the first layer
has already been deposited and move to deposit the 2nd layer.

The dipping will then proceed in the usual way until the number of layers required have been
deposited.

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Tutorial

Interpreting transfer ratios

Ideally, each time the substrate crosses the air-water interface, the surface of the substrate is
covered completely in monolayer, giving a transfer ratio of 100%.

In practice, though, this is rarely achieved. There are several reasons for this:

1. Collapsing monolayer - unstable film

The monolayer may be unable to support the dipping ('target') pressure and may be collapsing
away happily to itself. If such a film is deposited, the transfer ratio will be more than 100%
as the collapse rate will be superimposed on the dip rate.

The term 'collapse' is used generally to describe a film that is unable to support a given surface
pressure. The reasons for the collapse may be that:

a) the molecules are too hydrophilic and are being dissolved in the subphase. This can happen
at pressure as low as 8mN/m. Molecules can dissolve in the subphase ahead of the barrier and
reappear behind the barrier, i.e. they can exist in an equilibrium state between surfaces at different
pressures and the subphase.

b) the molecules may simply be leaking under the barrier. Check that all PTFE surfaces are clean
and that the barriers are resting firmly on the trough.

c) the film pressure is simple too high for the material and it is forming 'mountain ranges' on a
molecular scale on the surface. Remember that, for a 25Å long molecule, a pressure of 25mN/
m is equivalent to 100 atmospheres in the plane of the film! These molecular mountain ranges can
be observed by the naked eye just ahead of the barrier.

To check for film stability, hold the film at the target pressure while under pressure control and
watch the area v time plot. If the area value is decreasing linearly, this indicates that the film is unable
to support the pressure or that the film is leaking under the barrier. If the area value is decreasing
asymptotically to a constant area value, this indicates that the molecules are rearranging themselves
(annealing) into a more energetically favourable and stable order.

A stable film can be formed from arachidic acid on a 10-4M CdCl2 subphase. The area decrease
for such a film has been measured at less than 0.01cm²/min at 30mN/m.*

2. Film depositing and peeling off again

Suppose that the film is stable and that the first layer has been successfully deposited onto the
substrate with a transfer ratio of 100%. If the substrate now crosses the air-water interface for
the 2nd layer and the film peels off because it has not sufficient attraction to the first layer, a transfer
ratio of -100% will be recorded! If this sequence is continued for 10 layers, the inexperienced
observer may believe that 5 layers had been deposited when actually none have.

Watch the meniscus between subphase and substrate carefully. If it is curved the opposite
direction to the direction, then the previously deposited monolayer is peeling off.

* 'A modular, multi-functional LB trough', F.Grunfeld, Rev of Scientific Instruments, vol 64 (2) Feb 1993

56
 Tutorial

3. Partial peeling off of monolayer

Extending on case (2) above where 100% of the film peeled off again, consider the case where
only 50% peels off. If on 50% of the area, the film peels off and on the other 50% there is
deposition, then to the outside observer it appears that the transfer ratio is 0%. This can easily
happen on substrates that have not been cleaned properly.

Great care must be taken to avoid such a situation. A good indicator is always the meniscus
of the subphase on the moving substrate. If the curvature of the meniscus is uniform and follows
the direction of dipping, this indicates good deposition. If the meniscus 'dances' around i.e. its
radius of curvature is constantly changing, the substrate and/or subphase is probably very dirty.

Ensure that you do not report X or Z type deposition when you really have poor quality Y type!

Hence it always imperative that other evidence for the existence of the multilayer is obtained.
Note that some of the original X and Z type deposition observed was found to have Y type
structure, when checked for head group separation with X-ray diffraction (Gaines - 'Insoluble
monolayers'). The editor of this manual suspects that the some X and Z type layers that have
been reported in the literature are just plain bad Y type LB films!

4. Dip start and dip end positions

The setting of the dip start and dip end positions will also greatly influence the transfer ratio.

For conventional dippers (simple up and down motion), remember that even for ideal deposition,
the 2nd layer will not start being deposited until the meniscus has flipped over, which can be up
to 5mm worth of actual substrate movement. The 'meniscus radius' setting in the Dipper Menu
helps overcome this. If a radius of 5mm is chosen, then the TR calculation is performed from 5mm
after the 'dip start' position, thus eliminating this effect.

Figure 3.9: Substrate has to travel considerable distance, before meniscus flips over and
2nd layer starts being deposited. This can introduce large errors into transfer ratio
calculation.

Hence, the transfer ratios will differ considerably if the dip start position is set above the subphase
surface or below it.

Similarly for alternate layer dipper mechanisms, the transfer ratios are critically affected by the dip
start and dip end of both sides A and B.

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Tutorial

Good realistic plots for area/pressure v time and transfer ratios are given below:

Area, cm² Pressure,

mN/m
b

c d

Time, minutes

Transfer
ratio, %

No of layers

Figure 3.10: Area/pressure time plot and TRs of depostion with alternate layer dipper
a) compressing before dipping
b) first layer being deposited - a little too soon, as film is still annealing and
TR looks too high
c) 2nd layer better
d) film still collapsing a little in between dips
e) film now appears stable

58
 Tutorial

Operating a trough in 'coupled barrier' mode - option 'MC'

If you have 2 independent barriers, then the software may be used to move the monolayer across
the length of the trough using the 'coupled' mode. This is useful for scanning the monolayer under
a microscope or for the multi-compartment troughs, where the monolayer can be moved over
different subphases.

Typically, in this mode of operation, there are 2 compartments in the one trough which are filled
with differing subphases. The monolayer is spread and compressed in one compartment and then
transported into the second compartment, where some chemistry can be done over a different
subphase. If your trough also has a dipper, then the monolayer can also be transferred to a solid
substrate in the second compartment.

There are some extra function switches in this mode:

1. An 'A/B' switch to select between barrier 'A' and 'B'.

2. A 'SYM' button to switch between symmetrical compression (about the centre line of
the whole trough) and asymmetrical compression (within one compartment).

3. A 'coupled' mode in the 'Barrier' dialog box for moving the barriers in unison.

A typical run consists of:

1. Open barrier A by clicking on 'O' and making sure that the 'A/B' switch is set to 'A'.

2. Close barrier 'B' by switching over to 'B' and clicking on 'C'.

3 Click on 'STOP' when barrier B is over the compartment divider.

4. Spread the molecules in compartment A.

5. With the 'SYM' button set to 'NON SYM', select 'Isotherm' from the 'Barrier' dialog
box.
An isotherm will be made over compartment A.

6. 'STOP' before the monolayer collapses.

7. Select 'Coupled' from the Barrier dialog box.

The monolayer will be moved towards compartment B. Its speed is set as usual in
the 'Barr Speed' box and barrier B will be controlled so as to always keep the area
between the 2 barriers constant.

8. Click on STOP when the monolayer is over compartment B.

9. If you wish to dip, set up the dipper in the usual way and select 'Pi Control' from the
Barrier dialog box (making sure that the SYM button is still set to 'NON SYM'.

10. When the film is at target pressure, select Program Dip form the Dipper dialog box.
The monolayer will be deposited in the usual way.

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Tutorial

Operating a trough in alternate layer mode

Figure 3.11: Main Screen in Alternate Layer (AB) Mode

The main screen in the AB mode differs form the standard screen because there are, in effect, 2
separate troughs. So there are 2 independent barriers and 2 separate pressure sensors.

All the data and functions are available for both compartments. They are accessed by clicking on
the 'AB' switch (top left of the screen) to the compartment required. For instance, if you want to
zero pressure sensor A, switch to 'A' and click on 'Z'. If you want to open barrier B, switch to
'B' and click on 'O'.

All the displayed values such as area, pressure and dipper position are grouped in 2 columns 'A'
and 'B' and are displayed continuously.

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 Tutorial

A typical deposition run (alternate layer dipper)

1. Follow the instructions for the pressure-area isotherm first for compartment A. Repeat
for compartment B.
This will ensure that the trough is clean and ready to go.

2. Prepare a glass slide by rubbing it with the ferric stearate supplied.

This will make it hydrophobic.

3. Move the dipper to the top by clicking on 'F' (forwards) or 'B' (backwards).
The dipper will rotate continuously.

4. Click on 'STOP' when the dipper substrate carrier is at the top position (and the carrier
is horizontal).

5. Lay the slide on the substrate carrier, making sure it is held in place by the clips.

6. Go the Dipper Menu ('Dipper' in the menu bar).

7. Select the appropriate values for your deposition from the Dipper Menu below.
Typical values are displayed below.

8. Please see overleaf for an explanation of the dipper 'top end' & 'bottom end' positions.
These have to set to match the size of the substrate being coated.

9. Enter the sequence of 'A' and 'B' layers in the box and don't forget to enter the
corresponding 'Layers Required'.
The number counter allows you to check exactly which layer is which type.

Figure 3.12: Dipper Menu for Alternating Layer Dipper

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Tutorial

Alternate layer dipper 'top end' & 'bottom end' positions

substrate water

level

Top A Top B

Bottom A Bottom B

Figure 3.13: Alternate Layer Dipper 'Top' and 'Bottom' End Positions

The substrate is carried around the dipper - the arrows indicate the 'forwards' direction. The
critical positions are illustrated above.

'Top A' is just as the substrate is about to be immersed in side A - typically 75mm.

'Bottom A' is when it is just fully immersed in side A - typically 100mm.

'Bottom B' is just before it emerges on side B - typically 190mm

'Top B' is immediately after it has completely emerged on side B - typically 210mm

Typical values are for a standard 76 x 25mm glass microscope slide. Other size substrates have
different values, which are set before deposition commences.

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 Tutorial

10. Make sure that the dipper position is between '0mm' and 'top end A'.
If it is not, the layer counter may not start from zero.

11. Spread the monolayer in both compartments (as in the section 'taking an isotherm').

12. Select 'Pi Control' from the Barrier dialog box.

Both barriers will compress their respective monolayers.

13. Use the AB switch to view the compression in either compartment.

14. When both films are compressed to their target pressure, click on 'Program Dip'
(Dipper in the menu bar) to start the dipper in its pre-programmed sequence.
The dipper will move at the 'Inter Dip Speed' between immersions and at 'Dip Speed
A' when depositing monolayer A and 'Dip Speed B' at side B.

The dipper will continue until the layers have been deposited or there are not enough molecules
remaining on the surface in which case a warning message 'barrier too closed!' will appear. If this
happens, please open the barrier(s) and spread more molecules.

View the data also in the area & pressure - time axes and the dipper - area axes.

Save in the usual way.

Further Work
Try depositing on both glass slides and silicon wafers. LB films on silicon wafers give vivid
interference colours. Try different numbers of layers and making 'stepped' layers. Vary the
thickness and skeletonisation time of films on glass to improve the anti-reflection coating.

Conclusion
The tutorial is now over. You have followed in the footsteps of one of the founders of the Langmuir-
Blodgett technique and replicated one of the first attempts at a commercial application for a
Langmuir-Blodgett film. You should have gained at least a basic knowledge of Langmuir-
Blodgettry and some of the features and commands available on the Nima trough.

Many more details are given in the 'Software', 'Langmuir-Blodgettry' and 'Experiments' chapters.
We hope that you found this taste of the science of Langmuir-Blodgettry enjoyable. If you have
any problems or questions do not hesitate to get in touch with us at the address below- we will
be glad to help:

?@nima.co.uk

63
EXPERIMENTS
Nima 601S - Instructions & Experiments

Introduction
This chapter takes you through several experiments aimed at giving you a good working
familiarity with amphiphilic, mono-molecular films or 'Langmuir' films. It also gives advice on how
to prepare and operate the Langmuir trough.

The theory behind mono-molecular films can be found in the 'Langmuir-Blodgettry' chapter of this
manual.

It is assumed that your laboratory supervisor will have already set up your trough, so that you won't
have to set it up on the PC or calibrate anything. If it has not been set up, please see the 'Getting
Started' chapter of this manual.

This chapter (and indeed the whole manual) may be copied and distributed to students
- provided this is for educational purposes only.

Preparations
Before each experiment is carried out the film balance and materials which are to be used must
be prepared. Before any of the experiments are carried out, the film balance must have been
cleaned and calibrated as per the instructions below.

Safety
Before using any solvent, familiarise yourself with the relevant safety procedures.
Solvents must never be inhaled or touch your bare skin. Work in a fume cupboard when
making up the solutions. When making up solutions of metal ions such as cadmium,
always wash your hands afterwards to prevent accidental ingestion.

Check with your laboratory supervisor on safety regulations and correct disposal after
use. Remember you are responsible for your own and other's safety.

Materials
Solvents used to disperse surface active species should be as clean and pure as possible as should
all volumetric flasks and glassware which come into contact with them. Non-contaminating
methods should be devised for the weighing out and transfer of materials. Care should be taken
to ensure that all metal- and glass-ware are kept clean and kept only for use with the trough.

The water used in the film balance should be as pure as is possible. The quantity of particles, ions
and surface-active materials should be kept to such a low level that they will not significantly affect
the surface properties of monolayer systems.

General cleanliness
When studying mono-molecular layers which contain at most a few milligrams of material, even
a small amount of contaminant can cause serious errors. The trough, Wilhelmy plates and other
apparatus involved with the operation of the film balance must be kept as clean as possible.
Extraneous greasy material concentrates at the air-water interface; the source of such contami-
nation is usually grease from fingers or hair, this being transferred to the subphase by supposedly
clean instruments which have been handled. Clean tweezers should always be used and for all

66
 Nima 601S - Instructions & Experiments

operations it is advisable to wear disposable, powder-free polythene gloves. It is recommended

that the syringes used for deposition are cleaned in between use and that they are rinsed at least
once with the solution to be deposited. Clean laboratory coats should be worn, not only for
protection but also to prevent the deposition of fibres from clothing onto the subphase.

When not in use the trough should be kept empty of water, covered and out of direct sunlight.
If being moved, the pressure sensor should be removed from the trough to prevent accidental
damage.

The materials to be spread should be as pure as possible. Very small quantities of impurities,
especially surface active contaminants, can radically alter the molecular areas and can affect the
material’s film forming characteristics.

Cleaning the trough

The trough is fabricated from Polytetrafluoroethylene (PTFE), a material which will not contami-
nate the subphase. This polymer is essentially chemically inert, will not leach plasticiser and is the
most hydrophobic polymer known. PTFE can be subjected to very rigorous cleaning procedures.

Wipe the trough surface and barrier to remove loose dust and any contaminants present from
previous experiments. The barrier arm can be raised and the barrier lifted up for easy cleaning.
Wear powder free gloves and use a surfactant free 'Kimwipe' tissue soaked in chloroform for best
results. If you are not working in a fume cupboard (and/or safety regulations do not permit use
of chloroform), use a light alcohol such as ethanol or iso-propyl alcohol.

In general the best way of keeping the trough clean is to use it regularly and to avoid unnecessary
collapse of mono-molecular films. The tissues used to wipe the surfaces must be surfactant free,
for example, 'Kimwipes' type 7105, available from Kimberly-Clarke. Other tissues, even if they
are 'guaranteed 100% clean' may contain amphiphiles that prevent formation of pure monolayers.

Fill the trough with the cleanest available deionised water until it brims just over the top by about
2mm - giving plenty of leeway for water removal during surface cleaning. If the material to be
studied as a monolayer is changed, the trough should be emptied of water and thoroughly cleaned
in between each experiment.

Figure 4.1: Illustration of Nima 601S - pressure sensor is mounted at far end.

67
Nima 601S - Instructions & Experiments

Pressure sensor

Check the calibration of the pressure sensor:

1. Attach the empty weighing pan and zero the pressure reading.
2. Add the 100mg calibration weight.
3. The reading should now be -46.7 ± 0.5 mN/m.
4. If it is not, follow the instructions in the 'Calibrate Pressure Sensor' Menu.

Once the pressure sensor has been calibrated, a clean 'Wilhelmy plate' has to suspended from the
meter arm. If the pre-cut plates have run out, cut out a 22mm long and 10mm wide plate, from
a piece of filter paper.

Lower the Wilhelmy plate into the subphase so that it is just submerged and allow it to stand for
a couple of minutes. Ensure that the barrier is fully open (furthest away from the pressure sensor).
Zero the pressure sensor, first making sure that the filter paper is freely suspended at the air-water
interface. Check that raising the plate out of the water produces a pressure change of about 70
mN/m (the exact value for pure water in an atmosphere of saturated water vapour at 293K is 72.8
mN/m). If the change is within 5 or 6 mN/m, do not worry at this stage as the surface is probably
not yet clean. If the change is very much more or less, check the pressure sensor once more and
if necessary, repeat the calibration procedure.

Cleaning the subphase

Once the pressure sensor has been calibrated and set up with its Wilhelmy plate, begin to close
the barrier. The barrier should not be closed too quickly: for monitoring the cleanliness of the
subphase a speed of about 250cm2/min is recommended. As the barrier is being closed, watch
the pressure reading increase. Any pressure increase is due to contaminants on the subphase
surface. Once the barrier is closed to its minimum area, clean the subphase surface by means of
the PTFE nozzle (provided in the Monolayer Kit) connected to the suction pump. If the water level
drops below the bottom of the Wilhelmy plate, lower the plate until it is once more submerged.
Once the surface appears to be clean, open the barrier fully, re-zero the pressure sensor and close
the barrier. If no increases in surface pressure is observed on compression the surface can be
regarded as clean - if not repeat the cleaning and compressing processes.

Once the subphase is clean, open the barrier fully and cover the trough with its clear acrylic cover
to prevent contamination from the atmosphere.

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 Nima 601S - Instructions & Experiments

A typical pressure-area isotherm

The following steps are recommended to take an isotherm:

1. Clean the trough thoroughly witha Kimwipe (soaked in chloroform) and the plastic gloves
provided.

2. Make up a solution of 1mg/ml arachidic acid in chloroform.

3. Fill the trough with clean water.

4. Close the barrier(s) by clicking on 'C'.

- the barrier(s) will move to their 'close-to' position.

5. Aspirate the surface of the water enclosed by the barrier(s).

- keep your eye on the pressure reading.

6. Open the barrier(s) by clicking on 'O'.

-the barriers will move to their 'open-to' position.

7. Zero the pressure sensor by clicking on 'Z'

- the current surface tension will be defined as zero surface pressure i.e. 0mN/m.

8. Take an isotherm without molecules by clicking on 'Barrier' and 'Isotherm'

- the barriers will close and the isotherm will be displayed on the screen.
If the trough is clean, the curve will be horizontal on the X-axis. If there are
surfactants on the surface, a small rise in pressure will be observed at smaller
areas.
Please note that the axes are set to 'auto-scaling' and adapt themselves to the data
recorded.

9. Clean the surface again with the aspirator.

10. Zero the pressure sensor.

Whenever some water has been sucked out of the trough, it will have to be re-zeroed.

11. Open the barriers and spread the solution from the micro-litre syringe.
Wait for the pressure to return to 0.0mN/m - this indicates that the solvent has
evaporated. If the pressure does not return to zero, you have spread too much and
will have to remove some monolayer with the pump.

12. Take the pressure-area isotherm

- you should now see a good pressure area isotherm of arachidic acid on water.

13 Stop the barrier by clicking on 'STOP'

If you do not, the barrier will continue until it passes its 'close to' area and then
a message saying 'barrier too closed' will appear. The barrier will then be stopped
automatically.

69
Nima 601S - Instructions & Experiments

Experiment 1
The spreading of a monolayer & the visual observation of its
physical presence
Introduction

When a drop of oil is placed on a clean water surface it may behave in one of three ways:

1. It may not spread at all but remain as a 'lens' floating on the water surface.

2. It may form a thin film (sometimes called a duplex film) which spontaneously spreads and may
show interference colours - implying a thickness of hundreds of layers.

3. It may spread to form invisible monolayers, leaving excess oil in lenses on the monolayer surface
in equilibrium with the monolayer.

The spreading behaviour for any given material is determined by the difference between the
cohesion that its constituent molecules have for each other and the cohesion which they have for
the water molecules in the bulk of the subphase.

Stable monolayers are obtained with substances possessing both hydrophilic and hydrophobic
characteristics. Such molecules have an affinity for water at one end and a repulsion for water at
the other.

In studies of floating monolayers, such amphiphilic materials are often deposited onto the water
surface in solution. The solvents used are such that they are not miscible with water and yet are
volatile enough to evaporate completely at room temperatures leaving behind oriented amphiphilic
molecules.

The amphiphatic balance of the molecules under study is critical if they are to form floating
monolayers; hydrophilic head groups such as; -COOH, -OH, NH2 or -CN, when attached
to hydrophobic hydrocarbon chains of at least 14-16 carbon atoms in length will form oriented
layers.

Requirements

601S cleaned and calibrated, stearic acid (octadecanoic acid), chloroform.

Experimental

Make up approximately 5ml of 1mg/ml stearic acid in chloroform - the exact concentration is not
important.

Fill the trough with deionised water. It is interesting at this stage to observe just how high the water
meniscus can be above the (well cleaned) PTFE trough. Try filling it until it brims over. You should

70
 Nima 601S - Instructions & Experiments

be able to observe that the water level is up to 4mm above the level of the PTFE. (For an
explanation of this, go to the library and look up M.Lösche & H.Möhwald, Review of Scientific
Instruments, vol. 55 (1984) page 1968.)

Remove the water from the trough by means of the suction pump until it is level with the PTFE.
(It is a good idea to 'vacuum clean' the water surface while you're doing this - try to suck off all
the little bits of dust that invariably settle on the water surface.)

Close the barrier to 100cm² and start spreading the stearic acid solution dropwise from the syringe
in the 'active' part of the trough i.e. the end with the pressure sensor.

Initially, each drop will expand outwards, leaving the chloroform to evaporate and the stearic acid
molecules anchored on the water surface. After several drops however, the rate of drop expansion
will decrease dramatically until one drop will not expand at all and just float as a lens on the surface.
Spread just two or three more drops at different places at this point.

You should now see several droplets on the water surface 'locked' in place by the invisible
monolayer. Try gently blowing on the water surface. The droplets will move and return to their
original position - showing how elastic the monolayer is.

Now open the barrier to about 200cm² - the droplets will now expand and disappear from view.
The area has now increased, allowing more molecules to occupy the surface.

Repeat the experiment to check that the first result was no accident - add drops until lenses appear
and then increase the area once more.

Now slowly decrease the area to about 30cm². You will be compressing the monolayer all the
way to its 'collapse' - that is where it no longer is a monolayer. If you look at the surface carefully,
you will see a slight clouding of the surface and then some white streaks running parallel to the
barrier - these are agglomerations of collapsed stearic acid - rather like mountain ridges created
when the earth's tectonic plates collide.

Remove all the collapsed film from the trough.

Discussion

You should now have some appreciation of the physical idea of a monolayer. Think of its effect
on the water surface - what does it do to the surface tension? Repeat the above experiment with
the water level 4mm above the PTFE. Can you predict what will happen?

Finally, imagine life in two dimensions. How would you describe the effect of the suction pump
if you did not know of the existence of a third dimension?

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Experiment 2
The observation of molecular flow during compression

Aims of the experiment

The motion of a mono-molecular film on water surface can be difficult to visualise if the amphiphilic
material which has been spread onto the subphase is colourless. The movement of the mono-
molecular layer can be visualised by placing a powder such as talc onto the water surface and
observing the effect the floating monolayer has upon it as it spreads and as it is compressed.

Such observations, originally carried out by Henri Devaux, were reported by Irving Langmuir in
his paper 'Fundamental properties of solids and liquids II' J.Am.Chem.Soc 39, 1848, (1917).
It is also worth looking up B.R.Malcolm, Thin Solid Films, 178 (1989) 17 and H.Kumehara,
T.Kasuga, T.Watanabe & S.Miyata, Thin Solid Films, 178 (1989) 175.

This experiment uses the same techniques to aid observation of the behaviour of monolayers as
they are spread from solution, and as they are compressed and expanded by means of the barrier
on the film balance. The similarity of the mono-molecular film to a flexible membrane is
demonstrated.

Requirements

601S cleaned and calibrated, 4 clean 10ml volumetric flasks, chloroform, stearic acid
(octadecanoic acid), octadecanol, octadecylamide, octadecylamine, talc.

Experimental

Make up a 10 ml solution of approximately 1mg/ml of stearic (octadecanoic) acid in chloroform.

Ensure that the barrier of the trough is fully open and that the surface of the trough is free of
contaminants. Gently blow dust powdered talc onto the surface of the trough so that the entire
surface is covered by a thin talc layer.

Deposit one drop of the stearic acid solution into the centre of the trough. The solution should be
deposited from a very small height above the surface by means of a syringe which has previously
been rinsed with the spreading solution.

When the drop touches the subphase surface the talc will be immediately pushed back, forming
an area of apparently clear water. What effect does the gradually evaporating spreading solution
have on the apparently clean area?

Add a further drop of solution to another talc covered area of the trough. Does the second drop
behave in a similar manner? Does its addition cause any distortions to the first circle? If drops are
continuously added to an area where there is already a mono-molecular film present, the area of
the mono-molecular film will continue to expand until all the talc has been pushed to the sides of
the trough. What is the effect of adding further drops of stearic acid solution?

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 Nima 601S - Instructions & Experiments

If the barrier is closed the mono-molecular layer will be seen to push the talc covered water surface
in front of it towards the pressure sensor, the motion will be observed in the particles almost the
instant that the barrier begins to move. If no film was present the particles of powder would not
move until the barrier was very close enough to them.

Clean the surface of the trough thoroughly of all the talc and all the stearic acid monolayer by means
of the aspirator pump. Top up the water level and check that the surface is clean by running a 'blank'
isotherm without any molecules.

Once the surface is clean and the barrier fully open, deposit 4 drops of stearic acid solution in the
centre of the trough and allow it to spread until it covers a large area of the subphase, sprinkle talc
onto the monolayer covered surface only. Gently blow the dust covered film towards the
pressure sensor end of the trough. Slowly begin to close the barrier. The talc free area adjacent
to the barrier will become smaller until all the area between the barrier and the pressure sensor
end of the trough is talc covered. Once such a situation has been achieved stop closing the barrier
and make a note of the area 'A' to which the barrier has been closed.

If the barrier is closed further than 'A' the film will continue to be compressed for a while and unless
it is compressed too far, it will behave as a stretched membrane would. The monolayer can also
be expanded by opening the barrier, but only as far as area 'A'. If the barrier is opened further than
point 'A' the monolayer will cease to expand and will no longer follow the motion of the barrier.

Not all monolayer forming materials behave in the same manner as does stearic acid. Some
materials form much more viscous monolayer films which do not 'flow' as easily.

Interactions between the molecules themselves and between the molecules of the film and the
subphase are primarily responsible for the different flow behaviour which can be observed by
repeating the above experiment with different film forming materials.

Make up a solutions of similar concentrations to that of the stearic acid solution made up
previously, of octadecylamine, octadecanol and octadecylamide. With each material repeat the
second experiment - observing the manner in which the floating monolayer pushes the powder
particles while the barrier is being closed.

Discussion

Were any significant differences observed between the behaviour of the different amphiphiles
deposited? How can they be accounted for with regard to the properties of the hydrophilic end
groups? Could you suggest any modification which could be made to the trough in order to use
it to measure the viscosities of floating monolayers?

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Nima 601S - Instructions & Experiments

Experiment 3
Determination of the area occupied on the water surface by a
fatty acid molecule
Aim of the experiment

By monitoring the changes in surface pressure observed while compressing a stearic acid
monolayer a surface pressure-molecular area isotherm is constructed and the molecular area
of stearic acid is calculated.

Requirements

601S cleaned and calibrated, stearic acid (octadecanoic acid), chloroform.

Experimental

Make up a solution of stearic acid in chloroform; the concentration should be approximately 1mg/
ml. Make up 10mls of solution and note the exact concentration.

Draw up 50 micro litres of the solution into the syringe (which should have been rinsed several
times with the solution to be deposited) deposit the solution 'drop by drop' onto the water from
just above the surface. Leave the solvent to evaporate until the pressure returns to 0.0mN/m.

To prevent contamination during the course of the experiment make sure that the transparent cover
is on the trough.

Begin closing the barrier at a speed of about 250 cm²/min. As pressure begins to increase, slow
down the compression rate - to say 50cm².

As the barrier is closed further and the surface pressure begins to increase quickly, decrease
the speed further. Do not allow the surface pressure to increase much over 45 mN/m as the film
may collapse. Film collapse will be dealt with in more detail in another experiment.

Slowly open the barrier fully and repeat the compression process, once more taking care not to
compress the monolayer too much, again taking note of the surface pressure and area.

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 Nima 601S - Instructions & Experiments

Discussion

A floating monolayer will lower the surface tension of the subphase, The decrease in surface
tension is termed the surface pressure and this is the quantity which is being measured by
the pressure sensor. The surface pressure varies with the area and as the molecules on the
surface are behaving as a two-dimensional gas they can be described by the following relationship
(under ideal conditions):

PA = KT

Where 'P' is the surface pressure, 'A' the area, 'K' Boltzmann's constant and 'T' the thermodynamic
temperature. A surface pressure-area plot such as the one you are producing is known as an
isotherm as the compression is taking place under constant temperature. The shape of the isotherm
is characteristic of the surface-active substance being compressed. Every isotherm shows a
variety of different gradients and phases - each describing a part of the compression process as
the film becomes more and more ordered due to the pressure being applied to it by the barrier.

Stearic acid is a fairly 'classical' surface active material and its isotherm is not difficult to interpret.
Initially very little increase will be observed in the surface pressure as the molecules are randomly
distributed on the subphase surface with no ordering and are behaving as would be expected of
a two-dimensional gaseous phase. The above equation holds well in this phase.

Further reduction of the surface area leads to increases in the surface pressure as the inter-
molecular spacing in the subphase enter the range of the 1/r² coulomb forces. Also, the
hydrophobic chains which were originally oriented randomly near the surface of the subphase
begin to be lifted away from the bulk of the subphase. This state is usually called the 'liquid
expanded' phase.

When the surface area of the monolayer film is further reduced, the rate of increase of surface
pressure is even greater. An almost vertical linear relationship between surface pressure and area
characterizes the onset of the closely packed and highly ordered 'liquid-condensed' phase. In this
phase the stearic acid molecules are almost standing upright with the hydrophobic tail group nearly
perpendicular to the subphase.

The liquid-expanded and liquid condensed phases have been shown* to be just two of several
liquid crystal phases that a monolayer can exist in.

Plot the readings on a graph of surface pressure against area.

Knowing the volume of solution initially deposited on the subphase surface and the concentration
of the original solution, calculate the number of molecules which were deposited on the surface
of the subphase.

Calculate the area per molecule in Ångstroms (1 Ångstrom = 10-10 m) when the barrier is fully
opened, and the area per molecule when the barrier is fully closed.

Rescale the y-axis in terms of area per molecule.**

* I.R.Peterson, J Phys D, vol23, 1990, p379 ' Langmuir-Blodgett films'

** Your Nima software on the PC can of course do all this, but it is instructive to have done it yourself.

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Nima 601S - Instructions & Experiments

Figure 4.2: An idealised stearic acid isotherm showing molecular orientations

From the solid phase of the isotherm, when the molecules are closely packed it is possible to obtain
quantitative information on the molecular dimensions and shape of the molecule under study. The
molecular area (A0) can be obtained by extrapolating the slope of the 'solid' phase to zero pressure
(Fig 4.2) - the point at which the this line crosses the x-axis is the hypothetical area occupied by
one molecule in the condensed phase at zero pressure.

For a fully saturated alkanoic acid the molecular area determined in such a manner is 22-25 Å2,
Does the area which you calculated for stearic acid fall into this range? Such an area corresponds
to the cross sectional area of a hydrocarbon chain. This information first led Langmuir and others
to suggest that the compressed monolayer consists of closely packed vertically oriented chains.

How does the isotherm for the second compression differ from that of the first? If there are
differences how can they be accounted for?

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Experiment 4
Determination of the collapse pressure of a fatty acid.

Aim of the experiment

This experiment looks at what happens to a mono-molecular film when it is compressed past the
point when it behaves in an elastic manner. The collapse pressure (πc) of stearic acid is determined.

Requirements

601S cleaned and calibrated, stearic acid (octadecanoic acid), chloroform.

Experimental

Repeat Experiment 3, but this time continue to compress the stearic acid until the surface pressure
has climbed to a value over 40mN/m. Compress the film very slowly at this stage. Eventually the
surface pressure increase will stop, begin to level off and eventually fall sharply.

Look at the surface of the monolayer, it may be possible to see striations on the film surface, these
are areas of collapse. Open the barrier slowly and note the shape and position of the isotherm on
the x-axis. Compress the film again and note the area at which the film collapses and compress
an extra 50 cm². Relax and recompress the film.

Discussion

Plot a graph of surface pressure against area, the maximum of the isotherm is known as the collapse
pressure (πc) and for a saturated alkanoic acid such as stearic can have a value in excess of 50mN/
m.

At the collapse pressure some of the monolayer irretrievably loses its mono-molecular form. The
forces exerted upon it become too strong for confinement in two-dimensions and molecules are
ejected out of the monolayer plane to form a new phase. Molecular layers are piled on top of one
other resulting in disordered multilayers.

Figure 4.3: Illustration of monolayer collapse

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Nima 601S - Instructions & Experiments

The compressive forces which some monolayers can withstand are very high. If a molecule 25
Ångstroms in length is subjected to a force of 1mN/m in a compressed mono-molecular film,
calculate the three-dimensional equivalent force which would be acting on it.

What will be the three dimensional equivalent pressure acting on your molecule at the collapse
pressure determined in this experiment?

What effect did collapsing the film have on successive isotherms? Devise a model to validate your
experimental observations. How would you test that this model was any good?

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 Nima 601S - Instructions & Experiments

Experiment 5
Effects of structural changes in the hydrophobic tail group on
the isotherm.
Aim of the experiment
Changes within the structure of the amphiphilic material have a marked effect upon the monolayer
properties and hence on the shape of the isotherm. This experiment compares the pressure-area
isotherms of three fatty acids with hydrocarbon chains of different lengths, and two acids which
have the same number of carbon atoms in their hydrocarbon chains as stearic acid but have a
carbon - carbon double bond as part of their structure.

Requirements

601S cleaned and calibrated, 5 clean 10ml volumetric flasks, chloroform, stearic acid (octade-
canoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), Oleic acid (Z-
octadeca-9-enoic acid) and elaidic acid (E-octadeca-9enoic acid).

Experimental

Prepare solutions of stearic (octadecanoic, 17+1 C-units long) acid, arachidic (eicosanoic, 19+1
C-units long) acid, behenic (docosanoic, 21+1 C-units long) acid , oleic acid (Z-octadeca-9-
enoic acid) and elaidic acid (E-octadeca-9enoic acid). Each solution should be made up in
chloroform to an approximate concentration of 1mg/ml. The exact concentrations should be
noted. It is recommended that 10mls of solution are made up in each case.

Following the procedure outlined in Experiment 3, produce an isotherm for each species,
determine also the collapse pressure for each acid. In between each determination ensure that the
trough is thoroughly cleaned, small areas of collapsed film which are left by accident on the trough
can induce premature collapse in floating monolayers if they come into contact with them.

Discussion

The most used materials in Langmuir-Blodgett studies have been the long chain saturated
carboxylic acids which form very stable films and have therefore been very well characterised. In
order for an acid of this type to be capable of orienting itself at an air-water interface a hydrophobic
carbon chain of at least 13 carbon units long is required. Acids with hydrocarbon chains of lengths
less than that tend to be water soluble. Changes in hydrocarbon chain length down homologous
series are known to change the surface tension of a clean water surface to different extents. (An
approximation known as Traube's rule states that for a given homologous series of amphiphiles
the concentration required for an equal lowering of surface tension decreases by a factor of about
three for each additional CH2 group in the alkyl chain.).

What difference would you expect the different chain lengths to have on the molecular areas
determined from isotherms, such as that determined for stearic acid in Experiment 3?

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For each saturated acid calculate graphically an absolute molecular area. (Molecular area at zero
pressure). How do the molecular areas differ? Is this a surprising result?

The presence of a double bond within the structure of the hydrocarbon chain can have a marked
effect on the packing within a compressed monolayer.

Figure 4.4: Skeleton and space filling formulas of oleic, elaidic and stearic acids.
(Reprinted from 'Molecules for Langmuir-Blodgett film formation' Phil. Trans. R.Soc. Lond
A330, by R.Hann)

Oleic acid (Z-octadeca-9-enoic acid) and elaidic acid (E-octadeca-9-enoic acid) differ only in
the geometry of their unsaturated bond, both are related to stearic acid in that they all have 17
carbon atoms in their hydrophobic chains. The unsaturation has a great effect on their structures
as can be seen above and hence will have a large effect on the manner in which they will pack at
the air-water interface when compressed.

Plot an isotherm for each unsaturated acid and determine the absolute molecular areas. Are the
molecular areas of each acid of the expected magnitude? What can you deduce about the
orientation of each acid in the compressed film? What effect would a triple bond have upon the
packing within a monolayer if it were located in a similar position in a similar acid?

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Experiment 6
Observation of acid to salt conversion of an acid monolayer
ions in the subphase.
Aims of the experiment

The effect of adding divalent metal ions into the subphase on the isotherm of stearic acid is
investigated. The reaction between the monolayer and the metal ion containing subphase is carried
out at different zinc sulphate concentrations. The nature of the reaction and its effect on the
monolayers behaviour is discussed.

Requirements

601S cleaned and calibrated, stearic acid (octadecanoic acid), six 250ml volumetric flasks, zinc
sulphate, aluminium chloride.

Experimental

Make up a series of solutions of zinc sulphate, using the same deionised water which is normally
used to fill the trough. Then make up solutions of the following concentrations; 10-2M, 10-3M and
10-4 M . In each case make up 250 ml of solution. Take great care when handling zinc sulphate
and the solutions, zinc salts are irritants, the dust should not be inhaled; prolonged
exposure can lead to damage of eyes, lungs and kidneys.

Make up10ml of a solution of stearic acid in chloroform of a concentration of approximately 1mg/

ml. Note the exact concentration.

Following the procedure outlined in Experiment 3 produce isotherms of stearic acid on a clean
water subphase and then, using in turn each of the ZnSO4 solutions prepared earlier as a subphase.
The trough should be completely emptied in between experiments and cleaned. The cleanliness
of the subphase surface should be checked just as it was when the subphase was pure water.
Check with your laboratory technician for the correct procedure for disposal of the metal
ion solution.

Discussion

The alkanoic acids are weak acids (the pKa of stearic acid is approximately 4.7) and are therefore
very susceptible to ions in the subphase. Changing the pH of the subphase will have a marked effect
on the hydrophilic acid head groups. If the subphase is very acidic i.e. pH 4, the acid will not be
ionized and will therefore behave as an effectively neutral molecule. Due to dissolved atmospheric
carbon dioxide pure water quickly attains a slightly acidic pH of about 5.5. At such a pH ionization
will occur and carboxylate ions will be found in the film while hydrogen ions will be located in the
subphase.

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Nima 601S - Instructions & Experiments

R R R R

C C + Zn2+(aq) C C

O O- O O- O O O O
Zn

Figure 4.5: Reaction of Zn2+ with an alkanoic acid group

As would be expected, metal ions in the subphase will have a marked effect on the carboxylate
anions, and will therefore affect the monolayer properties. Singly charged cations of group 1
metals such as Na+ and K+, are particularly undesired, as the sodium and potassium salts of long
chain fatty acids can be fairly water soluble and these 'soaps' may even form micelles in the
subphase.

Divalent metal ions such as Zn2+, Ca2+, Cd2+ and Ba2+ have a marked effect on the monolayer
properties.

How do the isotherms differ from those produced on a water subphase? Can any trend be
observed due to the increasing Zn2+ concentration? Try 3 or 4 different concentrations ranging
from 10-3M to 10-4 M. Are the molecular areas calculated in each case different, and if so, why?

With increasing divalent metal ion concentration, the 'gaseous' part of the isotherm will be
extended towards lower molecular areas and the 'liquid expanded' phase will shrink. This is a result
of the reaction between the carboxylate ions and the zinc ions. Once each zinc ion has taken up
2 COO- , all the dissociated fatty acid will have been converted to its salt.

Repeat the experiment but this time using similar concentrations of AlCl3 in the subphase. How
does the presence of a trivalent metal ion affect the shape of the isotherm? How does the size of
the ion affect the calculated molecular area for the stearic acid? Does the way in which the film
flows on the water surface change with the addition of divalent and trivalent ions into the subphase?

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Experiment 7
A study of cholesterol films on water.
Aim of the experiment

The experiment determines the thickness of a floating monolayer of cholesterol. The molecular
area of the molecule in a compressed film is also calculated. From these results and knowledge
of the dimensions of the cholesterol molecule the approximate orientation of the molecule at the
air-water interface can be calculated.

Requirements

601S cleaned and calibrated, cholesterol, toluene.

Experimental

Make up a solution of cholesterol in toluene. Weigh out as accurately as possible 1mg of

cholesterol into a 10 ml flask and make up to the mark with toluene.

Once the trough has been cleaned, the pressure sensor zeroed, and the barrier opened fully, follow
the procedure described in Experiment 3 to record an isotherm of cholesterol. Deposit 50
microlitres of the cholesterol solution onto the water surface. Before closing the barrier allow the
toluene to evaporate for 10 mins as the toluene is far less volatile than the chloroform which had
been used to deposit the fatty acids and requires a longer time to evaporate.

Discussion

Figure 4.6: The structure of cholesterol

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Nima 601S - Instructions & Experiments

Although cholesterol may not immediately appear to be a material which can be studied as a
floating monolayer closer inspection reveals the presence of structural units vital for surface
activity: a hydrophilic head group, the -OH group, and a large quantity of hydrophobic unsaturated
hydrocarbon structure terminating in a six carbon unit long hydrocarbon chain.

Cholesterol's amphiphilic nature should not be surprising since, in common with other sterols, it
is commonly found in membranes in many higher organisms. Many studies have been carried out
on floating monolayers to elucidate the relationships between monolayers, bilayers and natural
membranes,

From the isotherm obtained determine the absolute molecular area of cholesterol. Assuming that
the cholesterol monolayer has the same density as a cholesterol crystal calculate the approximate
thickness of the compressed layer. Calculate the approximate dimensions of a cholesterol
molecule. (You will need to look up the lengths of bonds found in the molecule and the atomic radii
of various atoms; these can be found in most organic chemistry text books.)

From the very approximate calculations of film thickness and molecular area experimentally
determined, is it possible to deduce the orientation of the cholesterol molecules within the
compressed film?

Finally, try to relate what you have learnt about cholesterol and its popular (or not-so popular)
image. Do you think this image is justified? What would you do to control cholesterol
concentration in your blood?*

* You could discuss this in the bar after the practical (!).

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Experiment 8
The determination of the critical micelle concentration of
sodium sulphate from surface tension measurements.
Introduction

Micellar solutions are formed by the aggregation of materials such as fatty acids which are soluble
in both water and hydrocarbon solvents. Such surface active molecules ('surfactants') tend to
orientate themselves at the air-water interface. Typical of this class of materials is sodium dodecyl
sulfate or 'SDS':

CH3(CH2)11SO4- Na+

In dilute aqueous solutions the surfactants behave as a normal solute - i.e. ionic as a normal
electrolyte. When a specific concentration is reached, aggregates known as micelles are
formed. This concentration is known as the critical micelle concentration or 'CMC'. These
aggregates are roughly spherical and have the polar head groups pointing outwards:

Figure 4.7: Illustration of the structure of a typical spherical micelle in an aqueous

solution. Note all the polar head groups facing out and a minimum of internal space.

At the CMC, the physical properties of the solution change. There is more hydrogen bonding and
the colligative properties of the solution are altered, as are the electrical properties such as
conductivity.

Aim of the experiment

In this experiment the CMC of SDS is determined by monitoring the surface tension of an
aqueous solution SDS. A series of solutions is prepared and from the resulting plot of surface
tension v SDS concentration the CMC is determined.

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Nima 601S - Instructions & Experiments

Requirements

Film balance or tensiometer, suction pump for cleaning, sodium dedecyl sulphate, 1 clean 100ml
volumetric flask, 10 clean 20ml beakers, chloroform, Kimwipes.

Experimental

Make up a 20 mmol/dm3 solution of SDS and from that stock make up solutions of 1, 2, 4, 6, 8,
10, 12, 14, 16, 18 & 20 mmol/dm3 in the 20ml beakers. The MW of SDS is 288.

Starting with pure water and then the least concentrated solution and working up to the most
concentrated solution, measure the surface tension of each solution.

It is easiest to place the beaker with the solution under the pressure sensor and take the reading
by gently lifting the paper plate out of the solution.

Note the temperature at which each of the measurements are made.

Plot a graph of surface tension against concentration of SDS.

Discussion and Questions

From the graph, determine the CMC of SDS. The CMC occurs at the break in the curve.

The surface tension after the minimum should tend to a constant value as the surfactant molecules
have been removed into the micelles which are themselves not surface active and exist in the bulk
of the solution.

Micellisation is an alternative mechanism to adsorption at the surface for surface active molecules,
both decreasing the interfacial energy of the surfactant solution.

A value of the CMC of SDS at 40°C is quoted as being 8.6 mmol/dm3 on 'Surfactants and
Interfacial Phenomena' by M.J.Rosen, Wiley, 1978.

There is no sharp transition between pre- and post-CMC behaviours. Why is a minimum usually
observed?

How would the CMC be affected if the following were added?

1. Neutral salt.
2. An alcohol.

What effect would increasing the temperature of the solutions have on the CMC?

If an analog of SDS was used with a longer chain, what effect would that have on the CMC?

86
SOFTWARE
 Software

Introduction
This chapter is designed for reference only and need not be read completely. For a step by
step guide of actual trough operation, please see the Tutorial chapter.

The operating software is organised as a graphics screen (the 'active screen') and a series
of menus. All the 'action' takes place in the graphics screen in one of several axes such as
'pressure-area' as illustrated below.

Figure 5.1: Main Screen of Nima Software

The active screen

The active graphics screen appears at power up. The main part of the screen is taken up by
a graph. Then there is a menu bar running along the top with a series of 'drop down' menus.
In the top right hand corner the most recently loaded file name is displayed - initially this
is the 'standard' file. To the left of the graph is a margin displaying various sensor readings,
such as surface pressure and area.

Other functions are available from the 'menu bar' running along the top of the screen. These
menus are placed into logical groups such as 'File', 'Barrier', 'Dipper' etc.

Just below the menu bar are a series of large buttons. These are for often used functions such
as opening the barrier ('O') or moving the dipper up ('U') or down ('D'). The same functions
can be accessed via the menu bar. For instance to close the barrier, either click on the 'C'
button or click on the 'Barrier' menu and then 'Close'.

The Variables Menu in the box at the top left of the screen allows access to less often
changed variables, such as 'Target Pressure' or 'Cycle Max Area'. They can be changed by
clicking on their 'up' or 'down' arrows or typing in the new value.

94
 Software

Menu Bar
'File' Menu
Load Loads previously stored data
Save Saves current data - give file name
Print Gives print instructions - ALT-PrtScreen
Setup Setup Menu - explained in detail later in this chapter
Signature Nima address - in case you want to get in touch
Exit Exit the program

'Graph' Menu
Pressure-Area Selects pressure-area isotherm axes
P&A - Time Selects pressure and area - time axes
Dipper-Area Selects dipper-area axes (for deposition troughs only)
Transfer Ratio Selects Transfer Ratio axes (for deposition troughs only)
Change Axes Changes area axes between cm² and Ų/molecule
cm²<>Ų (to values entered in Monolayer Menu)
Clear graphs Clears all data in memory and from graphs

'Barrier' Menu
Monolayer Menu Selects Monolayer Menu - explained in detail later in this chapter
Open Moves barrier(s) to 'open to' area
Close Moves barrier(s) to 'close to' area
Isotherm Starts barrier moving and data logging
Pressuure control Compresses barrier(s) until target pressure is reached
Isocycle Starts barrier moving under iso-cycle (see Monolayer Menu)
Coupled Moves barriers in coupled mode (2B & MC option only)
Area control Compresses barrier(s) until target area is reached
Stop Stops barrier motor(s)

'Dipper' Menu
Dipper Menu Selects Dipper Menu - explained in detail later in this chapter
Dipper Up Moves dipper to top (or clockwise for alternate dipper)
Dipper Down Moves dipper to bottom (or anti-clockwise for alternate dipper)
Program Dip Starts pre-programmed dipping sequence
Dipper Stop Stops dipper motor

'Calibrations' Menu
Interface Test Runs interface diagnostic routine
Cali pressure sensor Self
Cali potential sensor evident
Cali temp sensor - all
Teach barrier pos explained
Cali barr speed later in
Cali dip speed this chapter!
Show cali data Displays current area and speed calibrations.

'Variables' Menu This menu changes the current variable available in the little box
at the top left of the screen. It is useful to be able to change these
'secondary' variables without having to stop and enter a full menu.
95
 Software

Buttons
Keyboard

C Closes barrier(s) to the 'close-to' area defined in the Monolayer Menu. Home

O Opens barrier(s) to the 'open-to' area defined in the Monolayer Menu. End

STOP Stops all motors Esc

D Down (conventional dipper only) moves dipper to bottom. PgDn

U Up (conventional dipper only) moves dipper to top. PgUp

F Forwards (alternate dipper only) moves dipper anti-clockwise.

B Backwards (alternate dipper only) moves dipper clockwise.

CLEAR Clears all data in memory and from graphs.

A-B A-B switch (alternate and multi-compartment troughs only)

Switches action between A & B (when zeroing, opening/closing or displaying data).

SYM Symmetry button (2 independent barriers AND single compartment only)

Switches between symmetrical and non-symmetrical compression of the barriers.

Z Zeroes pressure sensor (if AB switch present, then Z will zero either sensor A or B).

Permanently Displayed Variables

Barrier Speed
Sets the barrier speed for isotherms. The range is approximately 5cm2/min to 1000cm2/
min depending on trough type and gearbox ratio. It can be negative for expansions,
annealing, hysteresis loops etc. The barrier speed can also be set in the Monolayer Menu.

Cycles Required Done

Sets the number of isotherm cycles required (only when iso-cycle function is selected
in the Monolayer Menu). 'Done' displays the number already completed.

Dipper Speed up / down

Sets the dipper speed for depositions. The range is approximately 0.5mm/min to 50mm/
min depending on dipper type (and gearbox ratio). The dipper speed can also be set in
the Dipper Menu. For conventional dippers, separate 'up' and 'down' speeds are available.

Layers Required Done

Sets the number of layers required when dipping - can also be set in the Dipper Menu.
'Done' displays the number already deposited.

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Variables Menu - selectedly displayed variables

These can be displayed by selecting the variables from the menu in the rectangular box at the top
left of the screen.

Target pressure
This is the pressure at which the monolayer will be compressed to when running pressure
control - can also be selected in the Monolayer and Dipper Menus.

Feedback gain
This is the speed of response under pressure control. The greater this number, the faster
the barrier will compress the monolayer, according to the following algorithm:

Barrier speed = [feedback gain] * [target pressure - actual pressure ]

If feedback gain is too large, the pressure control will oscillate out of control.
Recommended values are 1.0 - 2.0 depending on aspect ratio of trough (the longer and
slimmer the trough, the higher the gain).

Dip Top End

Sets the position to which the substrate will be raised (can also be set in the Dipper Menu)

Dip Bottom End

Sets the position to which the substrate will be immersed (can also be set in the Dipper
Menu).

Cycle Max Area

The area to which the barrier(s) will be opened under iso-cycle control (but also check
the 'Cycle Min Pressure' in the Monolayer Menu).

Cycle Min Area

The area to which the barrier(s) will be closed under iso-cycle control (but also check
the 'Cycle Max Pressure' in the Monolayer Menu).

Target Area
This is the area at which the monolayer will be compressed to when running area control
- area control is selected in 'Barrier' in menu bar.

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Setup Menu
This is accessed from the 'File' Menu and allows you to configure the software to your
particular trough.

Figure 5.2: Setup Menu

Interface Enabled - YES if you want to control the trough.

NO if you want to run the software without the trough connected
(for example when evaluating data in your office)
Please note that on some PCs the software will run very slowly
when the interface is disabled AND there is no data loaded - so
the software always loads a default isotherm on power up when
the interface is disabled.

Serial port Selects the serial port on your PC that you have plugged the Nima
interface into.

Samples / Reading This allows the PC to average the data returning from the
interface, so the more samples the smoother the data, but the
slower the response. Recommended value: 5

Logging interval, secs This is the time before the data is 'logged' into memory. If you are
doing a long run, say overnight, you may wish only to log once
every minute, so that your data files won't become too big.
Typical value: 0.5 seconds.

Set Up Langmuir Trough Enters trough set up menu (described overleaf).

Enable Calibrations Gives access to 'Calibrations' in the menu bar.

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Trough Setup Menu

Figure 5.3: Trough Setup Menu

Dipper YES if you have a dipper; NO if you don't

Alternate layer dipper YES if you have an alternate layer dipper; NO if you don't

2nd independent barr. YES if you have 2 barriers with 2 motors

NO if you have only 1 motor (even if it's driving 2 barriers)

2nd pressure sensor YES if you have an alternate layer trough

NO for single compartment troughs

Temperature sensor YES or NO

pH sensor YES or NO

Surface potential sensor YES or NO

Advanced Setup Menu For custom made troughs

To access this menu, download version 5.17 from our website.

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Monolayer Menu
The Monolayer Menu is accessed from the 'Barrier' Menu and is shown below:

Figure 5.4: Monolayer Menu

This screen allows you to set up your isotherm run to your preferences. For instance you
may wish to take a single isotherm or perform isotherm cycles. You may wish to move the
barrier at a constant speed or in a 'quasi-static' way.

Entry of the molecular weight of your molecules, the concentration and volume of solution
spread enables the software to calculate the absolute number of molecules spread on the
subphase and hence convert the area on the subphase surface to an area per molecule.

TROUGH FUNCTIONS

Barrier speed The barrier speed of a compression run when taking an isotherm. Note that if you
want to do a 'relaxation' (opening the barrier), please enter a negative barrier speed
in the active screen.

Target pressure This the pressure that the film will be compressed to under pressure control
('Pressure control' under 'Barrier' in the menu bar).

'Close to' area This is the minimum 'allowed' area. If your barrier moves to a smaller area, it will
be stopped and 'barrier too closed' will be displayed. Click on 'O' to re-open it.

'Open to' area This is the maximum 'allowed' area. If your barrier moves to a larger area, it will
be stopped and 'barrier too open' will be displayed. Simply click on 'C' to close it.

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MOLECULAR PROPERTIES

Molecular weight Enter the MW of your molecule

Concentration, mg/ml Enter the concentration of your solution in mg/ml

Volume, µl Enter the volume of your solution in µl

Once the above data are entered, the computer can automatically label the area axes in area
per molecule. MW and concentration are only printed to 3 decimal places but can be entered
and are stored with greater accuracy.

A-B Switch between compartments (alternate layer mode only)

For an alternate layer trough (Model 622), molecule and solvent data are accessed one
compartment at a time. Use this switch to select between compartment 'A' and compartment
'B'.

ISOTHERM CYCLE FUNCTIONS

It is possible to program the barrier(s) to compress and expand the monolayer repeatedly
to observe hysteresis effects in isotherms. A choice of boundary conditions and the number
of cycles is given. It is possible to cycle between defined areas (in cm2) or defined pressures
(mN/m) or between one of each. Please note that the barrier will reverse on the first
parameter it meets, so you have to set both area and pressure parameters for the successful
functioning of this routine.

Example 1

If you wish to cycle through the 'liquid-expanded' phase of a fatty acid, set the limit for
minimum pressure to '0' mN/m and the limit for maximum pressure to about '30' mN/m. The
area limits should then be set at points well outside the areas corresponding to these
pressures, i.e. minimum area of 50 cm2 and a maximum area of , say, 500 cm2. (if you are
using a 600 cm² trough).

Example 2

If you wish to cycle between the gaseous phase and the liquid condensed phase, typical
values would be:

Max area: 500 cm2 (for a 600cm² trough).

Minimum π: -2 mN/m - better than 0 mN/m, as the pressure reading can on occasions drop
below zero.
Min area: 50 cm (or any low area value)
2

Maximum π: 45 mN/m - or whichever pressure you choose in the liquid condensed phase.

The barrier will then cycle between the max area and the max π limits.

Note - do not set the iso-cycle mode when dipping. Pressure will not be held constant
and monolayer transfer will be inhomogeneous.
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QUASI STATIC COMPRESSION

It is possible to make compression isotherms of monolayers 'quasi-statically' - that is to

move the barrier by a defined area, wait for a defined time and the move the barrier again.
This allows the monolayer to relax at each stage which is useful for stiff polymer films and
for collapsing films. It can also help to improve the determination of phase changes during
compression.

Select the size of area increment and the time interval between steps in this section. Then
click on 'Isotherm' under 'Barrier' in the menu bar to perform a quasi-static compression.

FILE Saving and loading

The operating conditions can be saved and recalled on their own. If a particular set of
conditions are frequently used, the 'standard' file can be overwritten to load these particular
conditions at power-up. Please note that only the operating conditions file are saved/loaded
here - no associated data files will be accessed.

Dipper Menu
The Dipper Menu is accessed from 'Dipper' in the menu bar and is shown below. This screen
allows you to set up your LB deposition to your preferences. For instance you may wish
to deposit a single layer or multiple layers. You may wish to move the dipper at a particular
speed and wait a certain time between layers.

Figure 5.5: Dipper Menu (for conventional dippers)

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Please note that the Dipper Menu for conventional LB dippers is shown here. The menu for the
alternating dipper is shown in the 'Tutorial' chapter.

Dipper speed The dipper speed is the speed with which the substrate crosses the interface.
Separate 'up' and 'down' speeds are available.

Target pressure This is the pressure that the film will be compressed to under pressure control.
When the monolayer is transferred to the substrate, the barrier will be moved to
keep the target pressure constant. This compensates for removal of monolayer
from the surface during dipping.

Top End This is the level that the substrate will be raised to.
Dipper position is measured in mm immersion from the top - so a dipper position
of 10mm means that the dipper is 10mm from the top. This is explained
diagrammatically overleaf.

Bottom End This is the level that the substrate will be immersed to.

Layers Required This is the number of layers that will be deposited.

Wait at Top This value determines how long the dipper will wait at the top of its cycle.

Wait at Bottom This value determines how long the dipper will wait at the bottom of its cycle.

Substrate Area This value is used to determine if, after completion of an 'up' stroke, there is
sufficient area left to deposit another 2 layers. If there is not, then 'Please open
barrier and respread...' is displayed.

It is also used in the transfer ratio calculation (as explained in the 'Langmuir-
Blodgettry' section). The substrate area is the total area immersed including both
faces and the sides of your substrate (if thick enough), less the meniscus radius.

Hence, for rectangular substrates:

substrate area = 2 * ((immersed length - meniscus radius) * (width + thickness))

Meniscus Radius This value improves the accuracy of transfer ratio calculations. It is best to
calculate the transfer ratio from the point at which the meniscus has 'flipped over',
rather than the dip start position, as explained above and in the 'Langmuir-
Blodgettry chapter.

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Setting 'top' and 'bottom' dipper positions - conventional dipper

The top and bottom positions are usually set so that the 'top' is where the substrate is entering
the water subphase and the 'bottom' is where it is immersed.

substrate water

(dipper jaws
not shown) level

Top Bottom

Figure 5.6: 'Top' and 'bottom' position for conventional dipper

Dipper Menu - alternate layer dipper

For alternate layer troughs the values of dip speed, target pressure and top & bottom ends are set
separately. So, separate values for side 'A' and 'B' are displayed.

The 'top' and 'bottom' positions are illustrated graphically overleaf.

In addition, the following values need to be set as well:

Inter Dip Speed

This is the speed the dipper will move at in between side 'A' and side 'B'. This saves time,
particularly when depositing large numbers of layers.

Alternate Layer Sequence

This is the sequence of layers deposited from side 'A' or side 'B'. Simply enter the
sequence you require in the box. The number control in the little box lets you check
exactly which number corresponds to which type of molecule.

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Alternate layer dipper 'top end' & 'bottom end' positions

substrate water

level

Top A Top B

Bottom A Bottom B

Figure 5.7: Alternate Layer Dipper 'Top' and 'Bottom' End Positions

The substrate is carried around the dipper - the arrows indicating the 'forwards' direction.
The critical positions are illustrated above.

'Top A' is just as the substrate is about to be immersed in side A - typically 75mm.

'Bottom A' is when it is just fully immersed in side A - typically 100mm.

'Bottom B' is just before it emerges on side B - typically 190mm

'Top B' is immediately after it has completely emerged on side B - typically 210mm

These typical values are for a standard 76 x 26mm glass microscope slide. Other size
substrates have different values, which are set before deposition commences.
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Calibrations Menu
All motors and sensors are calibrated at Nima before despatch. Once calibrated, it is
unlikely that the motors and potentiometers (position sensors) need to be calibrated again.
However, the full calibration proceedure is described here - just in case!

If you are updating your software, please load your new software into a new directory when
installing the new version and then copy the old calibration files ('sensors.cal', 'install.dat'
and 'standard.con') over to the new directory. This will save you having to recalibrate your
trough.

The following options are given in the 'Calibrations Menu':

Interface Test
Calibrate Pressure Sensor
Calibrate Potenial Sensor
Calibrate Temperature Sensor
Teach Barrier Positions
Calibrate Barrier Speed
Calibrate Dipper Speed
Show Calibration Data

In order to gain access to the Calibrations Menu, please enable it in the Setup Menu.

Interface Test
This displays the 'raw' data as sent by the interface to your PC. It is also possible to move
the motors 'manually' in this window. But take care - there are no safety stops and you can
crash your barrier / dipper and you may cause damage to the gearbox.

On entry, both interface and motors are disabled. Click onEnable Interface to start reading
the sensors. The INPUTS should be reading real data and the 'V2' light on the interface
should illuminate. If it does not, try changing the Serial Port No (bottom left of the screen).

Typical AD values are: pressure sensor: 10,000 - 20,000

barrier: 15,000 - 25,000
dipper: 15,000 - 25,000

Click on MOTORS DISABLED to allow access to the slider controls on the right of the
screen.

The following values apply: 0 ∇ 4095

open STOP close
up STOP down

ALWAYS STOP THE MOTORS BEFORE THEY REACH THE END OF

THEIR TRAVEL!

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Calibrate Pressure Sensor

It is good practice to check the calibration of the pressure sensor(s) before a series of runs,
particularly if the data is to be published. It can be quickly checked by attaching the
weighing pan and checking the indicated reading in mN/m for the calibration weight in the
active screen - remember that for a 21.0mm perimeter Wilhelmy plate, 100mg is equivalent
to -46.7mN/m.

To calibrate, select 'calibrate pressure sensor' from the 'Calibrations' menu and follow the
instructions given on the screen. The readings of the pressure sensor are recorded with the
empty weighing pan and with the calibration weight in the pan. These are then automatically
stored on disc. The 100mg calibration weight (the small metal tab) and pan are to be found
in the monolayer kit. Ensure that the correct calibration weight and plate perimeter are
entered in the appropriate boxes. It is good practice to check the calibration weight on a 6
figure balance.

Calibrate Surface Potential

The surface potential probe is plugged into the 'PB' socket at the back of the interface. The
surface potential option is enabled in the Setup Menu.

The software then guides you to bias the probe at two voltages 1.5V and 0.5V and the
equivalent reading of this stored. Please note that the absolute vale of voltage is not so
important, as long as the difference is 1.0V. So you could choose 2.0 and 1.0V as well.

More details are given in the Technical Appendix.

Teach Barrier Positions

The 'minimum area' and 'maximum area' positions of the barrier have to be 'taught' to the
PC. This is done by 'manually' moving the barrier to the correct position and then
confirming the position and equivalent area of that position.

The barrier is moved with a slider control provided on the screen. There is also a STOP /
CONTINUE button to instantly stop the barrier.

There are 4 different configurations for the various troughs made by Nima:

1. Standard - single barrier - Models 601A, 611M, 611D and 622(A&B separately)
2. 2 mechanically coupled barriers working symmetrically
- Models 601M, 601A/2B, 611M/2B, 611D/2B
3. 2 independent barriers working symmetrically but independently -Model 632/D1L
4. MC - 2 barriers with the ability to cross the centre line -Models 601/MC or 611/MC

These are explained in detail overleaf.

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Teach Barrier Positions (continued)

1. Single barrier

1234
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Barrier in 'closed' position Barrier in 'open' position

Figure 5.8: Teaching areas for single barrier troughs

The minimum area is the area at which the barrier is almost completely 'closed' - that is when
it is nearest the pressure sensor ('PS' in the above diagram). It is good practice not to run
the barrier to the end, so that when the minimum area is calculated, the curvature of the
corners of the trough can be taken into consideration, thus giving a completely accurate area
calibration.

To calculate the area, simply take an accurate ruler and measure the length x width. Please
note that standard troughs have exact widths of whole numbers like 10 or 20cm. Most
troughs have rounded corners of curvature of radius of 1cm. So ½.(4 - πr2) ( = 0.43cm²) has
to be deducted.

The maximum area is that area where the barrier is furthest away from the pressure sensor
and its trailing edge is just touching the edge of the trough. Again, measure the length x
width less the area of the rounded corners.

Please note in the case of 622 troughs with 2 barriers and 2 separate compartments, this
procedure is done twice, first for compartment A and then B (which has to use the same
areas).

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2. 2 barriers - symmetrical compression

PS
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centre line
Barrier A Barrier B

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Barrier A centre line Barrier B

Figure 5.9: Teaching areas for troughs with 2 mechanically coupled barriers with
symmetrical compression.

The minimum area is the area at which the barrier is almost completely 'closed' - that is when
it is nearly at the centre line and almost touching the pressure sensor (PS).

To calculate the area, simply take an accurate ruler and measure the length x width. Please
note that standard troughs have exact widths of whole numbers like 10 or 20cm.

The maximum area is that area where the barriers is furthest apart and their trailing (outside)
edges are just touching the edge of the trough. Again, measure the length x width.

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Teach Barrier Positions (continued)

3. 2 independent barriers
PS

centre line
Barr A open Barr A closed Barr B closed Barr B open
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B 1234
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Figure 5.10:
Teaching areas for 2 independent barriers for symmetrical compression.
A: Typical minimum and maximum positions for both barriers.
B: Calculation of minimum area
C: Calculation of maximum area

- note that the shaded is only half the area!

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The calibration procedure for 2 independent barriers is as follows:

1. Select 'Teach Barrier Position' from the Calibrations Menu and then click on 'A' for
barrier A.

2. Click on 'CONTINUE MOTOR' and let the barrier move to its 'closed' position, as
shown in Figure 5.10A.

3. Click on 'STOP MOTOR' when the barrier has reached its closed position. If
necessary adjust the position of the barrier by clicking on 'CONTINUE MOTOR'
and using the slider speed control to open or close it more slowly.

4. When it is at its 'closed' position, calculate the minimum area by measuring the area
enclosed, as shown in Figure 5.10B. Measure the distance from the centre line to the
leading edge of the barrier, as shown by the shaded area. Then double this area and
enter this value in the 'minimum area' box. You have to double the area, as it is the
area enclosed by the 2 symetrical barriers that is being measured.

5. Now click on 'ACCEPT' and then run the barrier to its 'open' position. Measure the
area as shown in Figure 5.10C from the centre line to the leading edge of the barrier.
Again, double it and enter that area into the 'maximum area' box.

6. Finally, perform the whole procedure for barrier B.

The only difference is that you will be given no choice of area to enter. So you have
to run barrier B to the same positions (but their mirror image of course) as barrier
A.

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Teach Barrier Positions (continued)

4. 2 barriers - crossing over for multiple compartment option

centre line
Barr A open Barr B closed Barr A closed Barr B open

B 123456789012
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Figure 5.11
Teaching areas for 2 independent barriers for multiple compartment operation.
A: Typical minimum and maximum positions for both barriers.
B: Calculation of minimum area
C: Calculation of maximum area
- note that the shaded is only half the area!

In this variation, the barriers can cross over the centre line so that the monolayer can be
compressed on one side and the transported over to the other. Hence the minimum area is
now across the centre line and is actually a negative number.

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The calibration procedure for 2 independent barriers crossing over is as follows:

1. Run barrier B to its fully open position (in the active graphics screen). It is now out
of the way.

2. Select 'Teach Barrier Position' from the Calibrations Menu and then click on 'A' for
barrier A.

3. Click on 'CONTINUE MOTOR' and let the barrier move to its 'closed' position, as
shown in Figure 5.11. This will be well over the centre line. Make sure the barrier
does not hit barrier B or its belt drive.

4. Click on 'STOP MOTOR' when the barrier has reached its closed position. If
necessary adjust the position of the barrier by clicking on 'CONTINUE MOTOR'
and using the slider speed control to open or close it more slowly.

5. When it is at its 'closed' position, calculate the minimum area by measuring the area
enclosed, as shown in Figure 5.11B. Measure the distance from the centre line to the
leading edge of the barrier, as shown by the shaded area. Then double this area and
enter this value in the 'minimum area' box. You have to double the area, as it is the
area enclosed by two barriers that is being measured.

6. Now click on 'ACCEPT' and then run the barrier to its 'open' position. Measure the
area as shown in Figure 5.11C from the centre line to the leading edge of the barrier.
Again, double it and enter that area into the 'maximum area' box.

7. Finally, perform the whole procedure for barrier B.

The only difference is that you will be given no choice of area to enter. So you have
to run barrier B to the same positions (but their mirror image of course) as barrier
A.

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Calibrating barrier speed

1. Select 'Calibrate Barrier Speed' from 'Calibrations' on the Menu Bar.

2. Click on Start and the calibration will run automatically.

Please ensure that the barrier is physically moving when 'moving at the slowest speed'. So,
when the software displays 'Moving Barrier at Slowest Speed', check that you can see the
position indicator actually decrease (slowly!). If it's not changing, increase the 'Min
Barrier Speed' from the default value of 50, until you can see it change. For greatest
accuracy, run this routine twice, if you have changed the Min Speed during calibration, so
that this speed is measured over the full 60 second calibration time.

Calibrating dipper speed

1. Select 'Calibrate Dipper Speed' from 'Calibrations' on the Menu Bar.

2. Check that the correct dipper stroke and dip factor have been entered. Typical values
are given below and will be written in your calibration certificate:

Dipper type Stroke Dip factor

mini 25mm 8.28

standard 75mm 4.10
alternate 38mm 1.006

3. Click on Start and the calibration will run automatically.

Please ensure that the dipper is physically moving when 'moving at the slowest speed'. So,
when the software displays 'Moving Dipper at Slowest Speed', check that you can see the
position indicator actually decrease (slowly!). If it's not changing, increase the 'Min
Dipper Speed' from the default value of 40, until you can see it change. For greatest
accuracy, run this routine twice, if you have changed the Min Speed during calibration, so
that this speed is measured over the full 60 second calibration time.

Calibrate Temperature Sensor

The temperatuure sensor is plugged into the 'pH/Temp' socket at the back of the interface
and the temperature option is selected in the Setup Menu.

The software then guides you to immerse the sensor at two temperatures (approx 5° and
50°C) and the readings of these are stored.

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Software Updates
Updates are regularly made available on our website - free of charge.

Please follow the instructionns on the website:

Downloadtheprogram This is the standard version 5.16 - the one that matches the 6th
edition of the manual Its size is about 2MB

Unzip the installation files. There are 4 files ‘zipped’ together. So you have to ‘unzip’ them
using ‘WinZip’ available from winzip.com (and often pre-installed on PC’s).

The file unzips to 4 smaller files (‘setup.exe’, ‘data.001’, ‘data.002’ and ‘Nima516help.txt’)
that fit onto 2 floppy discs. So you can copy and install it on another PC.

Set up. Click on Setup.exe and the Nima software will be installed for you. You can install
it to any directory and there are no dynamic link libraries to worry about.

If you are upgrading, please install the new software into a new directory, for instance,
'c:\nimanew'.

Then copy the 3 calibration files 'install.dat', 'sensors.cal' & 'standard.con' from your
exisitng 'nima' directory to the new one. This will save having to re-calibrate all the motors
and sensors.

Conclusion
If you read the whole section at one sitting - well done!

Otherwise, just use this section as a reference if you ever get stuck.

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TECHNICAL APPENDIX
Technical Appendix

Introduction
A list of frequently asked questions is presented in this chapter. These questions were
prepared by listening to several generations of research students learning their Langmuir
films at Cranfield University, England.

This chapter also explains the detailed functioning of the various motor and sensor
assemblies. If a problem does ever occur, please don't hesitate to contact us on:

?@nima.co.uk

Frequently asked questions

General

What does 'Barrier A/B too open/closed' mean?

The barrier has moved outside its 'allowed' range. This range is given by the 'open-to' and 'close-
to' areas, as set in the Monolayer Menu. Simply open or close the barrier to bring it into range by
typing 'O' or 'C' as appropriate.

Why does 'Pressure too low / too high' appear?

The value from the pressure sensor is outside its 'allowed' range of 0 - 2.5V. Usually, this
means that there is nothing hanging from the little suspension point. Just add the Wilhelmy
plate and you should be ok.

If this problem persists, check the 'Pressure Sensor' section, later in this chapter.

How full should the trough be?

The trough should be filled so that the water just brims over the top, say 2mm. The barriers
will work effectively over a wide range (at least ±2mm), because of the water’s surface tension.
A full trough allows plenty of leeway for cleaning without needing to top the subphase up.

When I switch the trough off, do I need to leave it in any particular state?
No, it doesn’t matter how the trough is left, though it is good practice to leave it empty and
thoroughly clean, with the barriers open and the dipper at the top for future users.

How do I start?
To take a pressure-area isotherm, select the 'Barrier' Menu from the Menu Bar and click on
'Isotherm'. The barrier(s) will move at the speed given in the 'Barrier Speed' control box, on
the left of the graph.

How do I escape from a command I don’t want to execute?

The 'ESC' key will STOP all motors moving. This has the same effect as clicking on the 'STOP'
button.

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 Technical Appendix

How do I clear the screen?

Click on the 'CLEAR' button or select 'Clear Graph' from the 'Graph' Menu on the Menu Bar.
A confirm will be requested, as this will wipe out all the data from your memory and the
graphs.

How often is the surface pressure / all data sampled?

Surface pressure (and all sensor inputs) are continually sampled. Usually 5 readings are taken and
these are then averaged and displayed on the screen. The number of readings can be changed in
the 'Set up' Menu, selected from the 'File' Menu on the Menu Bar.

How do I configure the trough for multiple users?

Install the software as many times as there are users. During installation, you are given a
choice of directory to load the software to. (The default directory is c:\Nima). Enter the
directory name of your choice and then run the software from that directory. You can, of course,
create the associated short-cuts and place them on the main screen of WIN95.

How can I display a directory of stored isotherms?

Use the 'Load' or 'Save' commands (from the File menu) which displays the contents of your
working directory. Click on 'Cancel' if you don't want to load or save anything.

The interface is not responding

Examine the connections of the serial lead to interface unit and to the computer. The most common
reasons for the interface not working are:

1. Wrong serial port selected.

Please try another serial port - there are 4 to choose from com1..com4. Usually com1
or com2 are used. Use 'Interface Test' from the Calibrations Menu to select the com
port.

2. Serial port driver clash with mouse or network.

If communications are intermittent and/or sluggish, the interrupts may not be set
properly in your PC set up. Check the System/Device Manager/ Ports/ Resources /
Interrupts in your WIN Control Panel.

Pressure sensors

Does the degree of waterlogging of the filter paper affect the pressure readings?
Yes, for a couple of minutes after the filter paper has been immersed, it will soak up water
and cause the pressure sensor reading to drift.

Does the length of filter paper used affect the pressure readings?
No, because the pressure sensors can be zeroed to offset the weight of the plate. The change in
force is all that is important.

How can I measure the pressure of a very stiff film?

This can be difficult with single barrier troughs.Try experimenting with the pressure sensor
position; putting pressure sensors on top of the barriers so that the measurement is made at the
point of compression prevents premature collapse of a rigid film. Of course, if you have a 2 barrier
trough, then the pressure sensor is mounted on the centre line of your trough and this problem is
eliminated.
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Technical Appendix

Why are the Wilhelmy plates being dragged towards the trough edge?
This could be because the floating Langmuir film is very stiff or it could be because of static charge
on the PTFE or the acrylic cover. In the latter case, try an anti-static gun or spray.

Why does the pressure sensor reading appear to drift slowly when the trough is first
used?
For a couple of minutes after the filter paper has been immersed, it will soak up water and
cause the pressure sensor reading to drift.

Why doesn’t the pressure sensor reading change very much?

The Wilhelmy plate may have fallen off or may be out of the water. If you suspect a hardware
fault, suspend the empty weighing pan from the sensor, zero the display and add the 100mg
calibration weight to the pan. The surface pressure should change by 46.7mN/m.

Isotherms

How can I plot a hysteresis loop?

There are 2 ways:
1. Compress as normal then use a negative barrier speed to run the expansion.
2. Select the isocycle function in the 'Barrier' Menu.
- the 'isocycle' parameters are set up in the 'Monolayer Menu'.

My isotherm appears vastly expanded/compressed / has vanished

Not all the run appears on the screen
It is likely that the isotherm has been loaded without choosing the 'auto-scaling' of the axes
set to 'auto'. Right-click over the graph and select 'auto-scaling' for both X and Y axes.
If you're running in alternate mode - check that you're in the right compartment (A-B switch
at top left).

How do I get a pressure-time plot?

Select 'Pressure&Area - Time' from the 'Graph' Menu on the Menu Bar. Then set the barrier
speed to 0cm2/min and click on 'Isotherm' on the Barrier Menu. The trough will be doing an
isotherm at zero barrier speed - i.e. a pressure-time plot.
Why do pressure-area isotherms occasionally have spikes?
This is probably because of external vibrations or air currents jolting the pressure sensors.
If spikes are visible on the screen, the Langmuir film will have been disturbed.

Why are pressure-area isotherms sometimes 'jumpy' / climbing in discrete steps?

The pressure sensor consists of a galvanometer movement. A suspension wire is attached to the
meter arm from which the Wilhelmy plate or balance pan hangs. The meter arm or suspension wire
can get slightly bent out of shape and catch on the inside of the meter housing. The resulting friction
causes jumpy rather than smooth changes in recorded pressure. Open the cover plate and free
the suspension wire with the tweezers provided.

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 Technical Appendix

Why does the pressure reading not return to zero / drop below zero when the
barriers are opened after a compression?
The surface was probably not thoroughly cleaned before spreading or the monolayer has
collapsed.

Why is the area-per-molecule wrong?

There could be several reasons. The solvent used may be miscible with water, carrying some
material into the water with it, the chemical may be impure (high purity materials must be
used), the concentration and volume of solution need to be checked, the film may be collapsing
prematurely, etc. Each possible cause needs to be investigated thoroughly and in a logical
sequence.

Dipping

What pressure do I dip at?

Generally, it is best to dip at in the liquid condensed phase, just above the liquid expanded-liquid
condensed transition point. At this point, the film is packed almost as tightly as it can be, yet minor
excursions in pressure will not result in premature collapse. Deposition can be monitored by
watching the meniscus as the substrate crosses the interface - an even meniscus usually implies
good transfer. The film must not, obviously, collapse at any stage.

Why are the transfer ratios wrong?

There are several possible reasons. If the substrate has not been properly cleaned and treated
prior to deposition, the film may be repeatedly deposited and peeled off the substrate. If the
'dipstart' and 'dipend' positions or the area have been wrongly entered, the computer will be
working from incorrect data.

It may be that the barriers are not sufficiently clean so that material is escaping under them.
It may be that the monolayer is collapsing continually under pressure - check this on the area-
time axes, while holding it at the deposition pressure. With a conventional dipper mechanism,
the 'up' and 'down' deposition ratios will always be different, as the meniscus will always
take a finite distance to reverse directions.

See also 'Interpreting Transfer Ratios' in the 'Tutorial' section of this manual.

Why does the barrier continually move inwards with pressure control on?
The floating monolayer could be collapsing, the Wilhelmy plate may be out of the water or
material may be escaping under the barriers if these are not clean.

How can I prevent the barrier of an unused compartment of an alternate layer trough
drifting to become 'too closed'?
If during deposition only one compartment of an alternate layer trough is used, the barrier for
the other compartment can slowly drift over a period of time and become 'too open' or 'too
closed'. This drift can be controlled by occasionally making the target pressure for the unused
compartment negative by adjusting it downwards using 'Target Pressure' controls (top left
of screen), accessed from the Variables Menu. Alternatively, the feedback gain can be set
to zero for the relevant compartment.

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Technical Appendix

Why does the dipper position not go through '0' mm?

With, for example, a standard alternate layer dipper mechanism attached the dipper position
jumps from around 250mm to around 10mm. This is because the potentiometer used to monitor
the dipper position has a dead area of a few degrees around 'top dead centre' (of the possible
measuring systems, this method nevertheless has the fewest drawbacks). A filter mechanism is
built into the software to prevent this from confusing the dipper control procedure.

Conclusion

We hope this has helped you with any questions or problems you may have had. The most
frequent problems we are asked about are the software settings. If you are in doubt, the
simplest thing to do is to re-install the software on your PC from the master diskette supplied
with your trough. This will have all the default settings and those specific to your trough included.

Please don't hesitate to contact us at Nima, if you still have problems:

?@nima.co.uk

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 Technical Appendix

Barrier Mechanisms
Introduction

The barrier mechanism for Nima Langmuir troughs consists of a PTFE barrier that is driven
along the trough by a toothed belt, as illustrated below:

spring loaded
arm
barriers

pulley
wheel

bolt
for clamp
clamp

pulley wheel

Figure A1: Barrier Assembly. Troughs can have 1 or 2 barriers - 2 barriers shown here.

Each PTFE barrier is located on the Langmuir trough by a spring loaded arm. This arm can
be raised to allow the easy removal of the barrier from the trough for cleaning.

The arm runs on a precision linear rail and is driven along the trough by means of a belt
mechanism. It is attached to the belt by means of a clamp, which is tightened by a bolt.

The belt mechanism is moved by a precision dc motor/gearbox combination turning a pulley

wheel at one end of the belt and the barrier position is detected by a potentiometer (called 'pot'
in this manual) attached to a second pulley wheel at the other end of the belt.

This following pages are written to help you repair or replace any components in case of
problems.

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Technical Appendix

Barriers - trouble-shooting

Symptoms

There are 2 major symptoms associated with a faulty barrier:

a) barrier not moving - either motor or gearbox faulty

b) barrier moving but area display incorrect - area not calibrated properly or potentiometer faulty

However, before you take everything apart, it is worth checking some obvious things first:

Wiring & connections

If your barrier is completely 'dead', check that the cables are plugged into their correct sockets
in the interface unit - barrier A into 'Barrier A' and barrier B into 'Barrier B'.

Check the wires at the motor and potentiometer - sometimes these can come loose but still be held
in place by the protective rubber sleeving. Just give each wire agentle tug, to make sure that it is
attached properly.

Mechanical action of barrier

Now check the mechanical action of the barrier. There is a hexagon bolt on the end of the barrier,
which tightens a small clamp onto the belt, Figure A1. When this is tightened, the barrier moves
along with the belt. When this is loose, the barrier can be pushed manually and should run freely
along the whole of its length. Please check that the barrier can do this.

If it is not running smoothly, please check for signs of scratching or pitting on the surface of
the barrier rail. Also check for any other obstructions interfering with the free movement of
the barrier.

Then move the barrier near the centre of its travel and tighten the locking bolt gently, so that
the belt is clamped firmly but not so tight that the belt is squashed out of shape.

Testing motor/gearbox

Symptoms of faulty motor/gearbox:

* Motor not responding under computer control - no noise, no movement

* Noise coming from motor but barrier not moving

Run the 'Interface Test' routine (under 'Calibrations' on the menu bar). The barriers are controlled
by slider controls on the right side of the screen. When the slider is in the middle, the barriers are
stopped. Moving them left and right makes the barriers move open or closed. There is also a
MOTORS ENABLED/DISABLED button which acts as an override for emergency stops.

Locate the appropriate barrier control ('A' or 'B') on the top right of the screen and move the slider
to the right. The barrier should move towards its 'closed' position - the further you move the slider
control from the middle, the faster the barrier will move.

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 Technical Appendix

Take great care not to leave the barrier moving. As there are no safety controls in this
test routine, the barrier can crash into its end stop and may be damaged. Always stop the
barrier!

Click on MOTORS ENABLED to stop it again.

If the barrier is not moving at all and there is no noise coming from the motor, it may be broken
and will have to be replaced. Please note these motors are usually very reliable and care
should be taken that everything is plugged in properly, before taking it all apart.

If there is a noise coming from the motor but the barrier is not moving, then the gearbox may be
broken and will have to be replaced.

Replacement of the motor/gearbox is described overleaf.

Testing the barrier potentiometer ('pot')

Symptoms of faulty pot:

* Area-time plot is non-linear

* Barrier not moving, even though motor/gearbox is ok
* Pot difficult to turn by hand (after belt has been removed)

If the barrier is moving without problems but the area display is inaccurate, the barrier may have
slipped on the belt. So, please re-calibrate the areas first, as described in the Software chapter
of this manual.

If the areas have been calibrated properly and the area display is erratic, please take an area-time
plot of the barrier position. Select the area & pressure v time axes and click on 'Isotherm' under
'Barrier' in the menu bar to take an area time plot. If you do not see a straight line of area-time,
then the pot is faulty and will have to be replaced.

Replacement of the pot is described overleaf.

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Technical Appendix

Replacement ot barrier motor/gearbox and potentiometer

motor plinth
gearbox

spacer
(must be orientated this way)
pulley wheel

slot
potentiometer
grub screw 'pot'

pot locking nut

Figure A2:
Exploded view of barrier assembly - showing motor/gearbox and potentiometer

1. Slacken the barrier clamp again and slip the belt out of the clamp.

2. Undo the grub screw of the pulleys (the little aluminium wheel with teeth for the belt)
attached to both the pot and the motor/gearbox. The grub screw is a little hexagon
socket screw that needs a 1.5mm hex key (supplied in our toolkit).
Note: if this grub screw is already loose, it may be that this is the problem. Tighten
it up and test the action of the barrier.

3. Using a 13mm (½ inch) spanner, gently loosen the locking nut that holds the pot to
the trough plinth (or the polished cover in a 601M). This will ease the tension in the
belt, as the pot is located in a slot, not a hole.

4. Gently pull the pulley wheels off the pot and gearbox shafts, so that the belt and pulley
wheels come away completely.

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 Technical Appendix

Replacement of motor/gearbox

1. Unscrew the 3 little screws holding the gearbox onto the trough plinth (or cover for
601M).

2. With the wires still attached to the motor, try to run it again. Is the output shaft turning?
If yes, try to stop it by hand - does the shaft stop turning? If yes, then maybe the gears
in the gearbox are slipping.

3. If only the gearbox is to be exchanged, then unscrew the 2 long screws that hold the
gearbox to the motor and replace with the new gearbox.

4. If the motor is to replaced, unsolder the wires from the motor, taking note of the wiring
configuration. This wiring configuration will depend on the gearbox and trough type
you have. But there are only 2 wires, so you can't go far wrong!

5. Replace the motor/gearbox assembly.

Replacement of pot

1. Completely unscrew the pot locking nut and remove the pot from the trough.

2. Disconnect the wires, making a note of the wiring configuration. This should be:

pin 1 red
pin 2 yellow
pin 3 blue

The red and blue wires may be switched over, depending on the direction of movement
of the barrier.

3. Replace the new pot, resolder the wires in the same way and fix it to the trough,
but don't yet tighten the pot locking nut completely.

Re-fitting the drive belt

1. With the pot locking nut still loose, attach the pulley wheels and belt as one unit, making
sure that the there is no undue force on the pot shaft. Too much force will damage the
bearing and cause the pot to jam up.

2. Now gently push the pot pulley wheel towards the end of the trough, so that some tension
is put on the belt - tight enough for the belt not to slip on the teeth of the wheels, but not
so tight that there is excessive force on the pot shaft. Then tighten the pot locking nut.

3. Now, while the barrier belt clamp is loose and not driving the barrier, move the barrier
motor with the slider control until the barrier '16 bit decimal INPUT' reads 25,000 ± 100
units. Then manually push the barrier to its 'open' position and gently tighten up the barrier
clamp.

4. Re-calibrate the areas, as described in the Software chapter of this manual.

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 Technical Appendix

Dipper Mechanisms
There are 2 Nima dipper mechanisms - conventional and alternate. In this context, 'conventional'
means that the substrate is oscillated vertically through the liquid-gas interface while the alternate
layer mechanism immerses the substrate through one monolayer and withdraws it from another.

Both dippers come in 2 standard sizes:

D1L-25 miniature dipper for small substrates up to 25mm long.

D1L-75 standard conventional dipper for microscope slides and 3" (75mm) wafers.
D2 - standard alternate layer dipper for microscope slides.
D2-3" large alternate dipper for 3" (75mm) diameter wafers.

The 'L' in 'D1L' stands for linear, to differentiate it from the old 'D1S' dipper which was
sinusoidal. This is now out of production.

Setting the Linear Dipper, Model D1L

The standard conventional linear dipper, Model D1L, consists of a substrate clamp that is
magnetically attached to an arm which is driven up and down by a belt and pulley system.

Dipper Potentiometer assembly

(expanded view)

top spacer (1 of 3)
magnetic holder flexible coupling
for substrate clamp
(clamp not shown)
dipper body
gearbox shaft

grub screw
pot shaft
motor
gear potentiometer - held
-box in place by 3 small screws

Motor/gearbox cover not shown

Figure A3: Illustration of Dipper, Model D1L-75

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 Technical Appendix

Setting the conventional dipper potentiometer position

1. First remove the round black cover by unscrewing the 2 screws..

2. Identify the flexible coupling which connects the pot to the gearbox, Figure A3. This has
4 little grubscrews - 2 pinching on the pot shaft and 2 on the gearbox shaft.

3. Slacken the 2 gearbox shaft grub screws with the 1.5mm hexagon key provided.
If access to the grub screws is not possible, rotate the dipper until it is.

Run the 'Interface Test' routine (under 'Calibrations' on the menu bar). The dipper is
controlled by a slider control on the right side of the screen. When the slider is in the middle,
the dipper is stopped. Moving it left and right makes the dipper move up or down. There
is also a MOTORS ENABLED/DISABLED button which acts as an override for emergency
stops.

Move the slider to the right. The dipper will move towards its 'down' position - the further
you move the slider control from the middle, the faster the dipper will move.

Take great care not to leave the dipper moving. As there are no safety controls in this
test routine, the dipper can crash into its end stop and may be damaged. Always stop the
dipper!

4. In the 'Interface Test' program, slide the 'Dipper' control to the left to move the dipper
to the top.

5. When it reaches the top i.e. when dipper height = 75mm for a standard dipper or 25mm
for a mini dipper, stop the motor by moving the slider to the centre.

6. If necessary, move the dipper down again by sliding the control a little to the right and then
back to the centre to stop it again. Repeat until the correct height is reached.

7. Check that the grub screws of the other side of the flexible coupling are tightened onto
the pot shaft and rotate the whole assembly so that the '16 bit decimal INPUT' on the
screen reads 25,000 ± 100 units.

8. Re-tighten the grub screws on the flexible coupling and replace the outer cover.

9. Quit the Interface Test program and click on 'Calibrate Dipper Speed':

Set the stroke and factor as follows: Dipper Stroke Dip Factor

D1L-75 75mm 4.10

D1L-25 25mm 8.28

If in doubt, check your calibrations certificate for the stroke and factor or contact us
- we keep records of your settings.

12. Click on START and the dipper speed will be calibrated as normal.
The dip factor and stroke will be saved along with the speed calibration data.

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Technical Appendix

Alternate Layer Dipper, Model D2

motor
housing

gearbox
housing

substrate

spring loaded seal

Figure A4: Alternate layer dipper, Model D2

The alternate dipper mechanism has its potentiometer in the smaller of the 2 stainless steel
housings. First, the dipper needs to be moved to its 'top' position:

1. Run the 'Interface Test' program.

2. Slide the dipper control to the left or right to move the dipper. It's not important which way,
as the substrate can go round indefinitely.
3. Stop when it reaches its top position by clicking on MOTOR ENABLED.
4. Undo the 2 screws holding the steel cover in place and remove the cover.
5. Loosen the 2 small screws holding the potentiometer in place.
6. Rotate the pot until its maximum value is displayed. In principle, this is 32,767, but
because of the 'dead band' of the pot, this is usually around 30,000. It is not important
if you have not adjusted it to the exact 'top dead centre' - as you will be setting the 'dip
start' and 'dip end' position in the Dipper Menu anyway.
7. Tighten the three little screws and replace the cover.

Then its speed needs to be calibrated:

1. In the main graphics screen, click on 'Calibrate Dipper Speed' under 'Calibrations' in the
menu bar.
2. For the standard D2 dipper, set the stroke to 49.0mm and dip factor to 1.006.
3. Click on START and the dipper speed will be calibrated as normal.
The dip factor and stroke will be saved along with the speed calibration data.

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 Technical Appendix

Pressure sensor, PS4

This pressure sensor is the fourth generation of our sensors. It combines very high accuracy with
stability and reliability. It uses a taut-band meter movement which gives very low friction.
The design of the electronic circuit allows infinite loop gain giving zero compliance i.e.
whatever the load, the Wilhelmy plate remains at the same level. Hence it is ideal for surface
tension measurements.

However, as a result of the small forces being measured, some of the component parts are
delicate and can be bent out of shape. This technical note aims to help the user repair the sensor
without having to return it to the manufacturer.

Mechanical setup

VR3 VR2

mini DIN
socket
detector
moving coil
infra-red diode end-stop
± 2mm

make sure that

detector this wire is
dangling freely

extension wire
with
suspension point

Figure A5: Illustration of PS4 - cover removed.

The sensor should be set up as in the diagram above.

For proper operation the following points should be observed:

1. The moving coil must be able to move freely .

2. The extension wire must be dangling freely and must not be touching the inside of the
housing.
3. The moving coil should reach the horizontal position when the sensor is powered up.

Electronic setup

There are 2 potentiometers to adjust:

VR2 offset of output signal - turn clockwise for increased output

VR3 gain of output signal - turn anti-clockwise for increased gain

When powering up, the coil should automatically reach its horizontal 'balance' position. There is
a wire end stop to prevent it moving by more than ±2mm from the horizontal, to keep it in range.

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Technical Appendix

If the meter does not come to its 'balance' position, push the diode a little towards the coil, so that
the optical signal (reflecting from the edge of the coil into the detectors) is a little stronger. Then
the electronics will take over.

VR2 (offset) and VR3 (gain) should be adjusted, so that the output level matches the appropriate
operating mode:

Suggested values are:

Force suspended from sensor Approximate output (Volts)

Tensiometers Troughs

Output with empty weighing pan: 0.2 0.8

Output with pan + 100mg: 0.6 1.6

Adjust the blue potentiometer labelled ‘VR2’ until 0.8V is displayed. Add the 100mg weight and
adjust VR3 until 1.6V is displayed. Remove the weight and check the output. Adjust VR2 again
if necessary. Repeat in an iterative manner until the required output voltages have been achieved.

Completion

Finally, replace the cover and calibrate in the usual way. Note that the voltages need not be set
exactly, as the sensor will be calibrated anyway. It is also possible to reduce the gain when wider
plates are used or increase the gain for greater accuracy.

Pressure sensor out or range -if this message appears, it means that the pressure signal has gone
outside the AD range. Usually this is not serious, as it only happens when there is no load on the
sensor i.e. when the plate and hooks have been detached. To prevent this occurring, simply
suspend a paper plate from the pressure sensor.

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 Technical Appendix

Temperature sensor

Any commercially available temperature sensing system can be used with Nima troughs.

If you want to log the data on the PC, there is an input on the Nima interface. The only criterion
is that the output of your meter be in the range 0 - 2.5V.

The following 'pin-outs' apply on the 'pH/Temp' input on the Nima IU4 interface:

pin 1 temp
pin 2 ground
pin 3 pH

Magnetic Stirrer, Model MST

The magnetic stirrer consists of a steel pin encased in an PTFE disc which is located in a 1mm deep
recess in the trough. It is rotated by rotating a magnet below the trough with a dc motor. Speed
control is effected from a small control box with a single turn dial. The wire from the motor is
plugged into the control box using the 5 pin DIN plug labelled ‘MS’.

Power is supplied to the control box from the 9V encapsulated supply. Usually a little '1 into 2'
box is supplied, so that the trough interface and the magnetic stirrer are supplied from 1 power
supply.

To operate, simply place the stirrer disc in its location on the trough and rotate the control knob
until the required speed is reached.

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Technical Appendix

Surface potential sensor - Trek Electrometer 320

Introduction

If you have bought a Trek electrometer (either separately or through Nima), the following
section will show you how to install it.

raisable
platform
guide

Knob to
raise or lower
sensor sensor head

vibrating electrode

Figure A6: Trek vibrating electrode mounted on Nima raisable platform

1. Carefully unpack the sensor and meter and set the sensor up as in the diagram above.
Read the Trek manual thoroughly.

2. Ensure that the sensitivity switch on the front panel of the meter is set to '10V' and
the NULL VOLTAGE switch to '+'.

3. Ensure that the RESPONSE dial on the back of the meter is turned all the way to 'slow'.

4. Lower the sensor head to its bottom position by rotating the knob on the back of the
body, so that the vibrating electrode is about 1mm above the ground plate.

5. Connect the probe lead from the sensor to the large plastic socket on the back of the
meter and the ground lead from the ground plate to the GND socket on the back of the
meter

6. Turn the meter ON.

7. Adjust the NULL VOLTAGE dial until the displayed reading is 0.00 V.
If the dial comes to the end of its range before 0.00 V is reached, flip the Null Voltage
switch over to '-' and continue the adjustment.

8. The unit is now ready for use.

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 Technical Appendix

When taking readings, keep the vibrating electrode as close as possible to the test surface without
actually touching it. The RESPONSE switch on the back of the meter can be adjusted to give
optimal compromise between speed of response and noise of signal.

Never touch the vibrating electrode - it may have a high potential on it.

Checking absolute potential against a reference

Take the 1.5V battery and place it in series with the earth wire between the GND socket and
the ground electrode, as in the diagram in below:

Sensor head Probe OUT GND

Trek 320 Control Unit

~ 1.5V

Figure A7: Electrical connections to test the surface potential sensor

A 1.5V potential step has now been placed on the plate and this should be displayed on the
meter. Remember to check the difference in voltage - not the absolute value. Check the battery
voltage with a conventional meter and compare the reading on the control unit. The change
noted on the meter should be within 10mV of the displayed signal.

Using with the Langmuir trough

I it is now necessary to lay the ground plate into the subphase, as otherwise the high surface energy
of the PTFE trough will swamp the small electric field of the monolayer. The ground plate also acts
as a reference for the surface potential signal.

1. Place the stainless steel ground plate in the (empty) trough and plug the 2mm 'banana'
connector provided on the earth lead to make good contact with the plate. The socket
on the plate connector consists of a 2mm stainless steel socket with a PTFE skirt. The
PTFE skirt prevents the connector from short-circuiting the monolayer.

There are 2 possible positions for the connector in the ground plate, depending on the
geometry of the trough. A single barrier trough should use the end position, while a 2
barrier trough should use the central position.

The other end of the ground lead has to be plugged into the 'GND' socket of the interface.

2. Connect the co-axial cable between the 'OUT' socket of the Trek meter and the 'PB'
socket' on the Nima interface.

135
Technical Appendix

3. Run the ‘Interface Test’ routine and check the ‘Pressure B’ reading. Adjust the output
voltage of the Trek with the voltage offset dial. Check that when the output display
reads 0.0V on the display of the Trek, 0.0V ±0.1V is displayed by the Pressure B
reading. Note that it is not important if the voltage displayed on the screen and the
Trek meter are not exactly the same - this is why you will be calibrating the output
precisely.

4. Go to the Setup Menu and enable the 'Surface Potential' option in 'Setup Langmuir
Trough'

5. Select the 'Calibrate potential sensor' from 'Calibrations' in the menu bar.
Follow the instructions on the screen: adjust the output on the Trek to read +0.5V, click
on the button to accept and then adjust it to read +1.5V and click again. The software
now knows what reading corresponds to a difference of 1V.

6. Isotherms of pressure and potential can now be captured, plotted and stored
simultaneously. Just click on 'Isotherm' to take the isotherm in the usual way.

Notes for best results

1. Compared to surface pressure measurements, changes in surface potential readings

are much more leisurely and need more experimental finesse. They require the same
kind of patience as do precise pH readings. Hence considerable care during operation
and interpretation is required.

2. It is easiest to make surface potential measurements of ionic solutions. Pure water is

a very good insulator and there are considerable higher stray (and variable)
capacitances on pure water subphases. Signal noise is proportional to the square of
ionic concentration.

3. Particular care must be made not to charge surfaces unnecessarily, as charges will
invariably leak to other surfaces near the probe and cause drift in the measured
readings. Ideally, antistatic protection should be worn (such as found in semiconduc-
tor fabrication areas) and antistatic mats should be placed around the trough bench.
In addition, a simple Faraday cage should be erected to prevent stray charges
interfering with measurements.

4. Place the vibrating plate of the probe about 2mm from the test surface. Should it touch
the water, remove the droplet with the aspirator and start again. If the probe is too far from
the test surface, the signal will be too noisy for satisfactory measurements. Don't be afraid
to experiment - no damage will be done to the probe.

136
 Technical Appendix

Cable connections

°)
5 pin DIN socket (240°)

3 - blue

black - 2 4 - yellow

green - 1 5 - red

Viewed from the outside of the interface unit or from inside the DIN plug.
(Pin numbers are marked on both plugs and sockets)

The colours identify the five wires used inside the six-wire screened cable running to
each motor/sensor.

The connections of the wires to the LB trough devices to the DIN plug/socket pins are
shown below. The potentiometers have pins marked 1,2,3 or a,b,c.

Device 601, 611 622 Alternate Conventional

Wire 622 side B side A Dipper Dipper D1L
Motor (+) green black green green
Motor (-) black green black black
Pot pin 1 or a red blue blue red
Pot pin 2 or b yellow yellow yellow yellow
Pot pin 3 or c blue red red blue

Pressure sensor PS4, mini DIN socket

Ground black (pin 2 on IU4 DIN socket)
-V white (pin 3 " " ")
Output red (pin 4 " " ")
+V yellow (pin 5 " " ")

137
Synthesis of ferric stearate
Ferric stearate is used to make the substrate surface hydrophobic (as described in the Tutorial
chapter). A small sample of this is supplied with your trough and it is also commercially available*.

If you prefer to synthesise it your own lab, the following process takes about an hour and a half:

- Make up a solution containing 1g of sodium stearate in 50ml of ultra-pure water.

- When all the solid has dissolved, pour the solution into a clean burette.

- Make up a second solution containing 0.3g of ferric chloride (iron (III) chloride)
hexahydrate in 50ml of ultra-pure water.

- When all the ferric chloride has dissolved, pour the solution into a second clean
burette.

- Simultaneously add the solution from each burette to a beaker containing

approximately 10ml of pure water.

Stop every few millilitres to gently stir the contents of the beaker and to check
that the pH of the resultant solution does not vary from pH7. If the pH is too acidic
the product of the reaction will be white stearic acid; if it is too basic, the product will be
dark grey ferric hydroxide. The reaction taking place is:

3C17H35COONa+FeCl3.6H2O
↓
Fe(C17H35COO)3(s) +3NaCl+6H2O

- On addition of all the reagents, stir the solution gently and leave to stand for a
few minutes. The ferric stearate should precipitate out of the solution as a pale brown
solid.

- Pour off the excess liquid above the ferric stearate.

- Wash the product with pure water a couple of times.

- Leave the product to dry in air on a filter paper for about an hour.

The yield of ferric stearate product should be 1g.

* Commercially available from TCI Co Ltd, Tokyo, Japan. Fax (+81)(3)3270 8466
INDEX
A of barrier positions 107
of barrier speed 114
Active screen 94 of dipper speed 114
software 94 of pressure sensor 107
Alcohol 18 of surface potential 107
Alkanoic acid weight 107
dissociation 30 Calibration certificate 114
Alternate layer deposition 66 Calibrations Menu 95, 106
Alternate layer dipper 130 Carboxylic acid 18
Alternate layer dipper enable 99 Change axes
Alternate layer mode 101 area units 95
Amines 18 Cholesterol
Amphiphatic balance 28, 76 monolayer properties of 89
Amphiphiles 76 Chromic acid 40
Amphiphilic 18 Clapham Common 20
Anti-reflection coating 48, 60 Cleaning 37, 73
Anti-vibration table 36 aspirator / pump 51, 74
Arachidic acid 49, 56 plasma etching 40
Area trough 36
per molecule 100, 121 water surface 51
Area control 95, 97 Cleanliness 35, 72
Argon ion plasma 49 for experiments 72
B Clear graphs 95
Clear memory 11
Babylonians 20 Clear screen 119
Bare skin 35 Close to area 100
Barrier 11 Coatings
hold time 100, 103 Anti-reflection 21
opening in software 94 Collapse
speed 100, 103 of monolayer 62
Barrier mechanisms 123 Collapse pressure 83
Barrier menu 11 Com port 119
Barrier positions Compression 53. See also Isotherm
calibration of 107 of monolayer 53
Barrier speed 96, 100, 114 Concentration 101
calibration 114 Containers
setting 53 For water 38
under pressure control 57 Contaminants 37
Barrier 'too open/closed' 118 Contamination
Bench space 2 surface active 38
Biotechnology 21 Copyright 72
Blank spreading 39 Coulomb 18
Blodgett 21 Coupled barrier operation 65
original paper 48 Cursor control 55
Boltzmann 25 Cycle Max Area 97
Bottom end 103 Cycle Min Area 97
Botttom position Cycles required 96
setting dipper 104
Buttons D
software 96 Decon-90 37
C Deposition 13, 56, 57. See alsoDipper
alternate layer 34
Cable connections 137 and peeling off 32, 62
Cadmium first monolayer
contamination 72 onto hydrophilic substrates 32, 61, 62
Cadmium arachidate 48 onto hydrophobic substrates 19, 31
Cadmium chloride 48, 87 head to head and tail to tail 33
Calcium fluoride quality 58
For IR studies 40 Types: X, Y and Z 33
Calibration Detergent Cleaning 37
Devaux, H. 21 G
Dip Bottom End 97
Dip Top End 97 Gaines, G.L. 21
Dipper 11 Gas detectors 21
adjustments 128 Gauges
making LB film 56 Step-thickness 21
mechanism Gelatin 20
questions 122 Gold
moving in software 94 Hydrophobic surface 40
Dipper enable 99 Graph
Dipper mechanisms changing type 54
setup 128 Graph Menu 95
Dipper Menu 11, 95, 102 Graphics
Dipper position 122 screen 94
Dipper positions Ground plate
setting top & bottom 104 for surface potential 135
Dipper speed 96, 103 Grunfeld, F 62
calibration 114 H
Dipper start/end
positions 63 Hardy 21
Dipper-Area graph 95 Head to head and tail to tail 33
Dipping 121 Helmanex 37
Display directory 119 Hexamethyl disilazane 40
Disposal HHTT 33
solvents 35 Homologous series
toxic materials 72 of fatty acids 85
Duplex film 76 Horizontal streaking
during deposition 32
E Hydrocarbon 18, 28
Easy cleaning 54 Hydrocarbon chain
Esc key 50 area 82
Exit software 95 isomers 85
length 29
F minimum length 85
Hydrophilic 18, 28
Fats 18
molecules in subphase 62
Fatty acid
surface preparation 40
dissociation 30
Hydrophobic 18, 28
saturated 83
surface preparation 40
unsaturated 85
tail structure 85
Feedback gain 11, 97
Hysteresis loop 120
Ferric stearate 49
hydrophobic surface 40 I
synthesis 138
File Ingestion 35
loading and saving 54 Installation 9
File Menu 95 hardware 4
Film balance software 8
cleaning 73 Interface 119
preparations 72 Interface Enabled 98
Film quality Interface Test
streaky 53 software 106
Filter paper 119. See also Wilhelmy plate Interface unit
Filters setting up 7
for clean labs 35 Interference colours 48
First layer Ionic equilibria 30
on up stroke. See Deposition Isotherm 12, 24, 50, 55, 82, 119, 120
Franklin, B. 20 arachidic acid 54
Fume cupboard 72 in tutorial 50
of similar fatty acids 85
Isotherm cycle 101
K spreading 76
stability 29, 62, 76
Kelvin probe viscosity 79
surface potential sensor 134 Monolayer Menu 95, 100
Kimwipes 12, 36, 49 Multi-compartment troughs 65
USA 14, 49 Multilayer 19, 56. See also Deposition
Kuhn, H. 21 Multilayer deposition
L in tutorial 56
Multiple users 10, 119
Laboratory
requirements 2 N
Langmuir, I. 21 Nature 21
Layers Required 96, 103 Non-centro-symmetric 34
LBfilm Non-linear optical films 34
deposition 56
Levelling 7 O
Lipids 18
Oleophilic 18
Liquid condensed phase 55, 56
Open to area 100
Liquid crystal 25
Operating Conditions Menu 52
Liquid expanded phase 55
Operating modes
Liquid-gas 18
multiple users 10
Liquid-liquid 18
Load file 95 P
Loading
operating conditions 102 P&A-Time 54, 59, 60, 95
Loading a file 13, 54 PC requirements 8
Logging interval 98 Peeling off
of monolayer 62
M Peroxide 40
Phase changes
Marbling 20
determination in monolayers 102
Materials
Piston oil 22
for experiments 72
Plasma etch 49
Memory
Plotting an isotherm 54
clear 11
Pockels, A. 21
Meniscus 31, 32, 58, 76
Polar media 18
during deposition 32, 58, 62
Port
Meniscus radius 59, 63
com port 119
Menu bar
Position detection 130
software 94
Potassium octanoate 37
Micelles 37
Potentiometer 123
Micro-balance 131
dipper 129
Möbius, D. 21
Powder
Molecular
monolayer flow 78
mountain ranges 62
Preparations
Molecular area
for experiments 72
determination 80
Pressure
zero pressure 25
equilibrium spreading 23
Molecular electronics 21
Pressure control 121
Molecular flow 78
for dipping 57
Molecular weight 101
setting 54
Monolayer
Pressure sensor 7, 118, 119
acid to salt conversion 87
adjustment 131
annealing 36
calibration 107
cholesterol 89
questions 119
collapse 25, 62, 77, 83
setup 131
elasticity 77
zeroing 51, 74
flow 78
Pressure sensor out or range 132
peeling off 62
Pressure too low 118
physical prescence 76
Pressure-area graph 95
reactions 87
Pressure-area isotherm 12
Pressure-time 120 Cadmium ions in 29
Print screen 95 cleaning 51, 74
Printing 13 metal ions in 87
Progrm Dip solution of molecules 62
software command 57 trivalent ions in 88
PS4 131 Substrate
PTFE 73 cleaning 40
Troughs 36 hydrophilic 31
Pump 2 preparation 49, 138
Pyroelectric films 34 Substrate area
calculation of 103
Q Sumi-nagashi 20
Quasi static compression 102 Surface
Questions 118 active 18, 37
cleaning 62
R with aspirator / pump 77
Rayleigh, Lord preparation 40, 138
John William Strutt 21 plasma etch 49
Refractive index pressure 23
changing in LB films 60 pressure too high 62
Removable top 5 Surface potential sensor 134
Repeated compressions 101. See also Isotherm cycles Surface tension 23
Requirements Surfactants 18, 37
for tutorial 48 Switching area axis
laboratory 2, 35 cm² <> A² 53
Run time variables 11 T
S Target area 95, 97
Safety 35, 72, 87 Target pressure 11, 97, 100, 103
Samples 119 setting for deposition 56
Samples / Reading 98 Teach barrier positions 107
Saving Tectonic plate
operating conditions 102 monolayer model 77
Saving files 13, 95 Temperature control 7
Schaefer 22 Tikopur 37
Sensors 21 Top End 103
Serial port 7, 119 Top position
Serial port driver 8 setting dipper 104
Setup Menu 95, 98 Transfer ratio 32, 60, 63, 121
Signature incorrect 121
software 95 Transfer ratios
Silk interpreting 62
waxed thread 22 Traube’s rule 29
Sodium hydroxide Trek electrometer 134
substrate preparation 40 Trivalent metal ion
Software 8, 94, 106 in subphase 88
active screen 94 Trouble-shooting
buttons 96 barriers 124
commands in tutorial 50 Trough
menu bar 94 filling 118
organisation 8 preparation 49
updating 10, 115 storage 58, 73
Solution transport 73
molecules in subphase 62 Trough top 5
Solvents U
boiling points 39
Soxhlet 40 Ultrasonic bath 40
Spreading 53, 76 Unpacking 3
Stop 11 Updating software 10, 115
Subphase
V
Van der Waal 18, 24
Variables
permanently displayed 96
Variables Menu 56, 95
Volatility
of solvents 39
Volume 101
W
Wait interval
dipping 103
Water 2, 38
Waveguides 21
Website 9
Weight
calibration 107
Whatman's
Chromatography paper 26
Wilhelmy plate 24, 26, 107, 120
setting up 7
X
X type deposition 63
X-ray diffraction
head group spacing 63
Y
Y type deposition 33
Z
Z type deposition 33, 63
Zero
pressure sensor 51
Zero pressure
molecular area 55
Technical Appendix

146